Polymer products and their use in cosmetic preparations

ABSTRACT

The present invention relates to polymeric products obtainable by mixing (A) polymers which are obtainable by free-radical polymerization of (A-1) ethylenically unsaturated monomers in the presence of (A-2) unsaturated polyalkylene glycols with (B) silicones at a temperature greater than or equal to 30° C. In addition, the invention relates to a process for the preparation of these polymeric products, and to their use in cosmetic preparations, in particular in hair cosmetic preparations.

The present invention relates to polymeric products, to a process fortheir preparation, and to the use of the polymeric products in cosmetic,in particular hair cosmetic, preparations.

Polymers with form-forming properties are used for cosmetic and/orpharmaceutical preparations and are suitable in particular as additivesfor hair and skin cosmetics.

In cosmetic preparations for the skin, polymers can develop a particulareffect. The polymers can, inter alia, contribute to the moistureretention and conditioning of the skin and to an improvement in the feelof the skin. The skin becomes smoother and more supple.

In cosmetic preparations for the hair, polymers are used for setting,improving the structure of and shaping the hair. They increase thecombability and improve the feel of the hair. These hair-treatmentcompositions generally comprise a solution of the film former in analcohol or a mixture of alcohol and water.

One requirement of hair-treatment compositions is to give the hair,inter alia, shine, flexibility and a natural, pleasant feel. The desiredprofile of properties includes strong hold at high atmospheric humidity,elasticity, ability to be washed out of the hair and compatibility withthe other formulation components.

DE 42 40 108 describes polysiloxane-containing binders which aresuitable as soil repellent coatings, in particular as antigraffiticoatings. However, these binders are paint-like and are not suitable forcosmetic purposes.

DE 16 45 569 describes a process for the preparation of organosilicongraft copolymers and their use as foam masses.

EP 0 953 015 describes amphiphilic polymers in combination withalkoxylated silicones.

JP 06-192048 describes copolymers of (meth)acrylamide-based monomers incombination with polyoxyalkylated siloxanes.

JP 10-226627 describes amphoteric polymers in combination withpolyoxyalkylated siloxanes.

EP 0 852 488 B1 describes cosmetic compositions which comprise asilicone-containing graft polymer in combination with at least onefurther silicone.

It is an object of the present invention to provide polymeric productswhich are suitable in particular for hair cosmetic preparations. Ofparticular importance was the combination of different advantageousproperties, such as strong hold at high atmospheric humidity,elasticity, ability to be washed out of the hair and compatibility withthe other formulation components. Furthermore, the product should givethe hair shine, flexibility and a natural, pleasant feel.

We have found that this object is achieved by polymeric products whichare obtainable by mixing

-   -   (A) polymers which are obtainable by free-radical polymerization        of (A-1) ethylenically unsaturated monomers in the presence of        (A-2) unsaturated polyalkylene glycols with    -   (B) silicones    -   at a temperature greater than or equal to 30° C.

In a particularly preferred embodiment, the silicones (B) used arecompounds which are chosen from the group consisting of (B-1) siliconeswith at least one quaternized or nonquaternized amine function, (B-2)silicone resins, (B-3) silicone rubbers, (B-4) polyalkoxylated siliconesand/or (B-5) silicone-containing polyurethanes (B-5).

All of the indices and substituents given below refer in each case tothe formulae which come directly before them in the text.

Ethylenically Unsaturated Monomers (A-1)

The suitable polymerizable monomers (A-1) used are ethylenicallyunsaturated monomers. In this connection, it is possible to use eitherindividual monomers or combinations of two or more monomers.

Monomers which may be polymerized by a reaction initiated by freeradicals are preferred. The term ethylenically unsaturated means thatthe monomers have at least one polymerizable carbon-carbon double bond,which may be mono-, di-, tri- or tetrasubstituted.

Polymerizable means that the monomers used can be polymerized using anyconventional synthetic method.

The ethylenically unsaturated monomers (A-1) can be described by thefollowing formula A-1a:X—C(O)CR⁷═CHR⁶   (A-1a)where

X is chosen from the group of radicals —OH, —OM, —OR⁸, NH₂, —NHR⁸,N(R⁸)₂;

M is a cation chosen from the group consisting of: Na+, K+, Mg++, Ca++,Zn++, NH₄+, alkylammonium, dialkylammonium, trialkylammonium andtetraalkylammonium;

the radicals R⁸ may be identical or different and are chosen from thegroup consisting of —H, C1-C40 linear or branched-chain alkyl radicals,N,N-dimethylaminoethyl, 2-hydroxyethyl, 2-methoxyethyl, 2-ethoxyethyl,hydroxypropyl, methoxypropyl or ethoxypropyl.

R⁷ and R⁶, independently of one another, are chosen from the groupconsisting of: —H, C₁-C₈ linear or branched-chain alkyl chains, methoxy,ethoxy, 2-hydroxyethoxy, 2-methoxyethoxy and 2-ethoxyethyl.

Representative but nonlimiting examples of suitable monomers (A-1) are,for example, acrylic acid and salts, esters and amides thereof. Thesalts may be derived from any desired nontoxic metal, ammonium orsubstituted ammonium counterions.

The esters can be derived from C₁-C₄₀ linear, C₃-C₄₀ branched-chain, orC₃-C₄₀ carbocyclic alcohols, from polyfunctional alcohols having 2 toabout 8 hydroxyl groups, such as ethylene glycol, hexylene glycol,glycerol and 1,2,6-hexanetriol, from aminoalcohols or from alcoholethers, such as methoxyethanol and ethoxyethanol, or polyethyleneglycols.

Also suitable are N,N-dialkylaminoalkyl acrylates and methacrylates andN-dialkylaminoalkylacrylamides and -methacrylamides of the formula A-1b

-   where R⁹=H, alkyl having 1 to 8 carbon atoms,-   R¹⁰=H, methyl,-   R¹¹=alkylene having 1 to 34 carbon atoms, optionally substituted by    alkyl,-   R¹², R¹³=C₁-C₄₀ alkyl radical,-   Z=nitrogen when x=1 or oxygen when x=0.

The amides may be unsubstituted, N-alkyl- orN-alkylamino-monosubstituted, or N,N-dialkyl-substituted orN,N-dialkylamino-disubstituted, where the alkyl or alkylamino groups arederived from C₁-C₄₀ linear, C₃-C₄₀ branched-chain or C₃-C₄₀ carbocyclicunits. In addition, the alkylamino groups may be quaternized.

Preferred monomers of the formula A-1b are N,N-dimethylaminomethyl(meth)acrylate, N,N-diethylaminomethyl (meth)acrylate,N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl(meth)acrylate.

Monomers (A-1) which can likewise be used are substituted acrylic acids,and salts, esters and amides thereof, where the substituents on thecarbon atoms are in the two or three position of the acrylic acid, and,independently of one another, are chosen from the group consisting ofC₁-C₄ alkyl, —CN, COOH, particularly preferably methacrylic acid,ethacrylic acid and 3-cyanoacrylic acid. These salts, esters and amidesof these substituted acrylic acids may be chosen as described above forthe salts, esters and amides of acrylic acid.

Other suitable monomers (A-1) are vinyl and allyl esters of C₁-C₄₀linear, C₃-C₄₀ branched-chain or C₃-C₄₀ carbocyclic carboxylic acids(e.g.: vinyl acetate, vinyl propionate, vinyl neononanoate,vinylneoundecanoic acid or vinyl t-butylbenzoate); vinyl or allylhalides, preferably vinyl chloride and ally chloride, vinyl ethers,preferably methyl, ethyl, butyl or dodecyl vinyl ethers, vinylformamide,vinylmethylacetamide, vinylamine; vinyl lactams, preferablyvinylpyrrolidone and vinylcaprolactam, vinyl- or allyl-substitutedheterocyclic compounds, preferably vinylpyridine, vinyloxazoline andallylpyridine.

Also suitable are N-vinylimidazoles of the formula A-1c, in which R¹⁴ toR¹⁶, independently of one another, are hydrogen,

C₁-C₄-alkyl or phenyl:

Further suitable monomers (A-1) are diallylamines of the formula A-1d

where R¹⁷═C₁-C₂₄ alkyl

Further suitable monomers (A-1) are vinylidene chloride; andhydrocarbons with at least one carbon-carbon double bond, preferablystyrene, alpha-methylstyrene, tert-butylstyrene, butadiene, isoprene,cyclohexadiene, ethylene, propylene, 1-butene, 2-butene, isobutylene,vinyltoluene, and mixtures of these monomers.

Particularly suitable monomers (A-1) are acrylic acid, methacrylic acid,ethylacrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate,n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexylacrylate, decyl acrylate, methyl methacrylate, ethyl methacrylate,propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate,t-butyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate,methyl ethacrylate, ethyl ethacrylate, n-butyl ethacrylate, isobutylethacrylate, t-butyl ethacrylate, 2-ethylhexyl ethacrylate, decylethacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropylmethacrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylates,2-hydroxyethyl methacrylate, 2-hydroxyethyl ethacrylate, 2-methoxyethylacrylate, 2-methoxyethyl methacrylate, 2-methoxyethyl ethacrylate,2-ethoxyethyl methacrylate, 2-ethoxyethyl ethacrylate, hydroxypropylmethacrylates, glyceryl monoacrylate, glyceryl monomethacrylate,polyalkylene glycol (meth)acrylates, unsaturated sulfonic acids, suchas, for example, acrylamidopropanesulfonic acid;

acrylamide, methacrylamide, ethacrylamide, N-methylacrylamide,N,N-dimethylacrylamide, N-ethylacrylamide, N-isopropylacrylamide,N-butylacrylamide, N-t-butylacrylamide, N-octylacrylamide,N-t-octylacrylamide, N-octadecylacrylamide, N-phenylacrylamide,N-methylmethacrylamide, N-ethylmethacrylamide, N-dodecylmethacrylamide,1-vinylimidazole, 1-vinyl-2-methylimidazole, N,N-dimethylaminomethyl(meth)acrylate, N,N-diethylaminomethyl (meth)acrylate,N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl(meth)acrylate, N,N-dimethylaminobutyl (meth)acrylate,N,N-diethylaminobutyl (meth)acrylate, N,N-dimethylaminohexyl(meth)acrylate, N,N-dimethylaminooctyl (meth)acrylate,N,N-dimethylaminododecyl (meth)acrylate,N-[3-(dimethylamino)propyl]methacrylamide,N-[3-(dimethylamino)propyl]acrylamide,N-[3-(dimethylamino)butyl]methacrylamide,N-[8-(dimethylamino)octyl]methacrylamide,N-[12-(dimethylamino)dodecyl]methacrylamide,N-[3-(diethylamino)propyl]methacrylamide,N-[3-(diethylamino)propyl]acrylamide;

maleic acid, fumaric acid, maleic anhydride and its monoesters, crotonicacid, itaconic acid, diallyldimethylammonium chloride, vinyl ethers (forexample: methyl, ethyl, butyl or dodecyl vinyl ethers), vinylformamide,vinylmethylacetamide, vinylamine; methyl vinyl ketone, maleimide,vinylpyridine, vinylimidazole, vinylfuran, styrene, styrenesulfonate,allyl alcohol, and mixtures thereof.

Of these, particular prefrence is given to acrylic acid, methacrylicacid, maleic acid, fumaric acid, crotonic acid, maleic anhydride, andits monoesters, methyl acrylate, methyl methacrylate, ethyl acrylate,ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, t-butylacrylate, t-butyl methacrylate, isobutyl acrylate, isobutylmethacrylate, 2-ethylhexyl acrylate, N-t-butylacrylamide,N-octylacrylamide, 2-hydroxyethyl acrylate, hydroxypropyl acrylate,2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, alkylene glycol(meth)acrylates, unsaturated sulfonic acids, such as, for example,acrylamidopropanesulfonic acid, vinylpyrrolidone, vinylcaprolactam,vinyl ethers (e.g.: methyl, ethyl, butyl or dodecyl vinyl ethers),vinylformamide, vinylmethylacetamide, vinylamine, 1-vinylimidazole,1-vinyl-2-methylimidazole, N,N-dimethylaminomethyl methacrylate andN-[3-(dimethylamino)propyl]methacrylamide; 3-methyl-1-vinylimidazoliumchloride, 3-methyl-1-vinylimidazolium methylsulfate,N,N-dimethylaminoethyl methacrylate,N-[3-(dimethylamino)propyl]methacrylamide quaternized with methylchloride, methyl sulfate or diethyl sulfate.

In a very particularly preferred embodiment, the monomers (A-1) used aret-butyl acrylate and methacrylic acid.

Monomers with a basic nitrogen atom can be quaternized in the followingway:

Suitable for quaternizing the amines are, for example, alkyl halideshaving 1 to 24 carbon atoms in the alkyl group, e.g. methyl chloride,methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, propylchloride, hexyl chloride, dodecyl chloride, lauryl chloride and benzylhalides, in particular benzyl chloride and benzyl bromide. Furthersuitable quaternizing agents are dialkyl sulfates, in particulardimethyl sulfate or diethyl sulfate. The quaternization of the basicamines can also be carried out with alkylene oxides, such as ethyleneoxide or propylene oxide, in the presence of acids. Preferredquaternizing agents are: methyl chloride, dimethyl sulfate or diethylsulfate.

In a preferred embodiment, the monomers (A-1) used are (meth)acrylates.

The quaternization can be carried out before the polymerization or afterthe polymerization.

In addition, the reaction products of unsaturated acids, such as, forexample, acrylic acid or methacrylic acid, with a quaternizedepichlorohydrin of the formula A-1e (R¹⁸=C₁ to C₄₀ alkyl) can be used.

Examples thereof are, for example:(meth)acryloyloxyhydroxypropyltrimethylammonium chloride and(meth)acryloyloxyhydroxypropyltriethylammonium chloride.

The basic monomers can also be cationized by neutralizing them withmineral acids, such as, for example, sulfuric acid, hydrochloric acid,hydrobromic acid, hydroiodic acid, phosphoric acid or nitric acid, orwith organic acids, such as, for example, formic acid, acetic acid,lactic acid, or citric acid.

In addition to the abovementioned monomers, the monomers (A-1) used maybe so-called macromonomers, such as, for example, silicone-containingmacromonomers with one or more free-radically polymerizable groups oralkyloxazoline macromonomers, as are described, for example, in EP 408311.

Furthermore, it is possible to use fluorine-containing monomers, as aredescribed, for example, in EP 558 423, compounds with a crosslinkingaction or compounds which regulate molecular weight, in combination oron their own.

Unsaturated Polyalkylene glycols (A-2)

Suitable as compounds (A-2) are unsaturated polyalkylene glycols of theformulaH₂C═CH—C_(c)H_(2c)—O—(C₂H₄O)_(a)(C₃H₆O)_(b)—R⁵   (A-2a)and/orH₂C═CH—C_(c)H_(2c)—O—(C₄H₈O)_(a)—R⁵   (A-2b)in which

R⁵ is —H, —CH═CH₂, —(CH₂)_(s)—CH═CH—(CH₂)_(t)—H, a straight-chain orbranched alkyl group having 1 to 12 carbon atoms, a straight-chain orbranched alkoxy group having 1 to 6 carbon atoms, a straight-chain orbranched acyl group having 2 to 40 carbon atoms, —SO₃M, a C₁₋₆-aminoacylgroup optionally substituted on the amino group, —NHCH₂CH₂COOM,—N(CH₂CH₂COOM)₂, an aminoalkyl group optionally substituted on the aminogroup and on the alkyl group, a C₂₋₃₀-carboxyacyl group, a phosphonogroup optionally substituted by one or two substituted aminoalkylgroups, —CO(CH₂)_(d)COOM, —COCHR⁷(CH₂)_(d)COOM, —NHCO(CH₂)_(d)OH, —NH₂Yor a phosphate group

-   -   the groups M, which are identical or different from one another,        are hydrogen, Na, K, Li, NH₄ or an organic amine,    -   R⁷ is hydrogen or SO₃M,    -   d is in the range from 1 to 10,    -   s may be 0, 1 to 10    -   t maybe0, 1 to 10    -   a is in the range from 0 to 50,    -   b is in the range from 0 to 50,    -   a+b is greater than 0,    -   c is 0, 1, 2, 3 or 4,    -   Y is a monovalent inorganic or organic anion.

Particular preference is given to compounds (A-2) where R⁵═H and/or astraight-chain or branched alkyl group having 1 to 12 carbon atoms, inparticular —CH₃ and —C₂H₅.

Particular preference is given to compounds (A-2) where c=1.

Very particular preference is given to compounds (A-2) where R⁵═H andR⁵═—CH₃.

Very particular preference is given to compounds (A-2) where R⁵═H andc=1

Very particular preference is given to compounds (A-2) where R⁵═—CH₃ andc=1

Compounds (A-2) are available commercially, for example under the tradenames Pluriol from BASF AG. Examples which may be mentioned are theproducts Pluriol® A 10 R, Pluriol® A 11 R.

Likewise suitable are the compounds which are obtainable under the CASNo. 272 74-31-3 polyalkylene glycol monoallyl ether or under the CAS No.126682-74-4 as polyalkylene glycol monovinyl ether from Clariant(description of A-and V-type polyglycols from Clariant).

Silicones (B)

Suitable silicones (B) are in principle all silicone compounds.Nonvolatile silicones are particularly suitable. Nonvolatile siliconesare those compounds with a boiling point above 90° C., in particularabove 100° C. Water-soluble or water-dispersible silicones areparticularly suitable.

For the purposes of the invention, water-dispersible silicones meanssilicones which, upon contact with water, within 24 hours form a fluidwhich does not allow any solid particles to be detected with the eyewithout optical devices. To check whether a silicone iswater-dispersible, 100 mg of the silicone, in the form of a 100 mm thickfilm, are placed in 100 ml of water (20° C.) and shaken for 24 hours ona commercially available shaking table. If, after shaking, solidparticles can no longer be seen, but the fluid possesses turbidity, thesilicone is water-dispersible; in the absence of turbidity, it isreferred to as water-soluble.

In a preferred embodiment, the silicones used are compounds which arechosen from the group consisting of (B-1) silicones with at least onequaternized or nonquaternized amine function, (B-2) silicone resins,(B-3) silicone rubbers, (B-4) polyalkoxylated silicones and/or (B-5)silicone-containing polyurethanes. It is of course possible to useeither mixtures of compounds within an individual group (e.g. 2compounds from B-4) or else mixtures of compounds from different groups(one compound from B-1 and one or more compounds from, for example,B-4).

(B-1) Silicones with at Least one Quaternized or Nonquaternized AmineFunction

Among the silicones which comprise at least one quaternized ornonquaternized amino group, mention may be made of:

(a) the silicone polymers which correspond to the formula B-1a:R¹ _(a)G¹ _(3-a)—Si(OSiG² ₂)_(n)-(OSiG³ _(b)R² _(2-b))_(m)—O—SiG⁴_(3-a)-R³ _(a)   (B-1a)in which:

G¹, G², G³ and G⁴, which are identical or different, are a hydrogenatom, a phenyl group, OH, C₁-C₁₈-alkyl, for example methyl,C₂-C₁₈-alkenyl or C₁-C₁₈-alkoxy;

a, a′, which are identical or different, are 0 or an integer from 1 to3, in particular 0;

b is 0 or 1 and in particular 1;

m and n are numbers whose sum (n+m) can vary particularly between 1 and2000 and in particular 50 and 150, where n can be a number from 0 to1999 and particularly from 49 to 149 and m can be a number from 1 to2000, particularly from 1 10;

R¹, R², R³, R⁴, which are identical or different, are a monovalentradical of the formula C_(q)H_(2q)O_(s)R⁵ _(t)L, in which q is a numberfrom 1 to 8, s and t, which are identical or different, are 0 or 1, R⁵is an optionally hydroxylated alkylene group and L is an optionallyquaternized aminated group which is chosen from the following groups:

-   -   NR″—CH₂—CH₂—N′(R″)₂    -   N(R″)₂    -   N′(R″)₃A⁻    -   N′H(R″)₂A⁻    -   N′H₂(R″)A⁻    -   N(R″)—CH₂—CH₂—N′R″H₂A⁻,        in which R″ is hydrogen, phenyl, benzyl or a monovalent        saturated hydrocarbon radical, e.g. an alkyl radical having 1 to        20 carbon atoms, and A⁻ is a halide ion, such as, for example,        fluoride, chloride, bromide or iodide.

(b) the compounds of the formula B-1b:NH—[(CH₂)₃—Si[OSi(CH₃)₃]]₃   (B-1b)

This compound corresponds to the CTFA name“Amino-bis-propyldimethicone”. The products corresponding to formulaB-1a are, for example, the polysiloxanes, which are referred to in CTFAnomenclature as “Amodimethicones” and correspond to the followingformula B-1b:

in which x′ and y′ are integers which depend on the molecular weight andare generally those whose molecular weight is between 5000 andapproximately 20 000. A product which corresponds to the formula B-1a isthe polymer named in CTFA nomenclature as“Trimethylsilylamodimethicone”, which corresponds to the formula B-1d:

in which n and m have the meanings given above (cf. formula B-1a). Acommercial product which corresponds to this definition is a mixture(90/10% by weight of a polydimethylsiloxane withaminoethyl-aminoisobutyl groups and a polydimethylsiloxane which is soldunder the name Q2-8220 by DOW CORNING. Such polymers are described, forexample, in the patent application EP-A-95238.

Other polymers which correspond to the formula B-1a are siliconepolymers of the formula:

in which:

-   -   R⁷ is a monovalent hydrocarbon radical having 1 to 18 carbon        atoms and in particular a C₁-C₁₈-alkyl radical or C₂-C₁₈-alkenyl        radical, e.g. methyl;    -   R⁸ is a divalent hydrocarbon radical, particularly a        C₁-C₁₈-alkylene radical or a divalent C₁-C₁₈-alkenoxy radical,        e.g. C₁-C₈;    -   Q⁻ is a halide ion, in particular chloride;    -   r is a statistical average value from 2 to 20 and in particular        from 2 to 8;    -   s is a statistical average value from 20 to 200 and in        particular from 20 to 50.

Such polymers are described in particular in the U.S. Pat. No.4,185,087.

A polymer which corresponds to the formula B 1b is the polymer which issold by Union Carbide under the name “Ucar Silicone ALE 56”. If thesesilicone polymers are used, a particularly interesting embodiment istheir use together with cationic and/or nonionic surfactants. Forexample, it is possible to use the product sold under the name “EmulsionCationique DC 929” by DOW CORNING, which, apart from the amodimethicone,comprises a cationic surfactant which comprises a mixture of productsaccording to the following formula:

in which R⁹ is alkenyl and/or alkyl radicals having 14 to 22 carbonatoms, derivatives of tallow fatty acids, together with a nonionicsurfactant of the formula: C₉H₁₉—C₆H₄—(OC₂H₄)₁₀—OH, known under the CTFAnomenclature “Nonoxynol 10”.

Another commercial product which can be used according to the inventionis the product which is sold under the name “Dow Corning Q2 7224” by DowCorning which, together with the trimethylsilylamodimethicone of theformula B-1d, comprises a nonionic surfactant of the formula:C₈H₁₇—C₆H₄—(OCH₂CH₂)_(n)—OH, in which n=40, otherwise referred to asoctoxynol-40, a further nonionic surfactant of the formula:C₁₂H₂₅—(OCH₂—CH₂)_(n)—OH, in which n=6, otherwise referred to asisolaureth-6, and glycol.

(B-2) Silicone Resins

The silicon resins which can be used according to the invention arecrosslinked siloxane systems which comprise the units: R²SiO_(2/2),RSiO_(3/2), and SiO_(4/2), in which R is a hydrocarbon group which has 1to 6 carbon atoms, or is a phenyl group. Among these products,particular preference is given to those in which R is a lower alkylradical (C₁-C₆) or a phenyl radical.

Among these resins, mention may be made of the product which is soldunder the name “DOW CORNING 593”, or any products which are sold underthe names “SILICONE FLUID SS 4230” and “SS 4267” by GENERAL ELECTRIC andwhich are “dimethyl/trimethylpolysiloxanes”.

(B-3) Silicone Rubbers

The silicone rubbers (B-3) according to the invention arepolydiorganosiloxanes of high molar masses between 200 000 and 2 000000, which are used on their own or in a mixture in a solvent which ischosen from the volatile silicones, the polydimethylsiloxane oils, thepolymethylphenylsiloxane or the polydiphenyldimethylsiloxane oils, theisoparaffins, methylene chloride, pentane, the hydrocarbons or theirmixtures.

Preference is given to using a silicone rubber with a molecular weightbelow 1 500 000. The silicon rubbers are, for example, apolydimethylsiloxane, a polyphenylmethylsiloxane, apoly(diphenylsiloxan-dimethylsiloxane), apoly(dimethylsiloxane-methylvinylsiloxane), apoly(dimethylsiloxane-phenylmethylsiloxane), apoly(diphenylsiloxane-dimethylsiloxane-methylvinylsiloxane). Thesesilicone rubbers can terminate at the end of the chain withtrimethylsilyl or dimethylhydroxysilyl groups.

In particular, a silicone rubber may be used which corresponds to theformula B-3a:

in which:

-   -   R¹, R², R⁵ and R⁶, together or separately, are an alkyl radical        having 1 to 6 carbon atoms,    -   R³ and R⁴, together or separately, are an alkyl radical having 1        to 6 carbon atoms or an aryl radical,    -   X is an alkyl radical having 1 to 6 carbon atoms, a hydroxyl        radical or a vinyl radical,    -   where n and p are chosen such that the silicone rubber has a        viscosity greater than 100 000 mPa.s, preferably greater than        500 000 mPa.s.

In general, n and p can have values from 0 to 5000, preferably from 0 to3000. The silicone rubber can be incorporated into the composition as itis or in a form dissolved in silicone oil, such as a volatile ornonvolatile PDMS (polydimethylsiloxane).

Silicone rubbers which can be used according to the invention may be anyin which:

-   -   the substituents R¹ to R⁶ and X is a methyl group, p=0 and        n=2700, such as that which is sold under the name SE30 by        General Electric,    -   the substituents R¹ to R⁶ and X are a methyl group, p=0 and        n=2300, such as that which is sold under the name AK 500 000 by        Wacker,    -   the substituents R¹ to R⁶ are a methyl group, the substituent X        is a hydroxyl group, p=0 and n=2700, in a 13% strength solution        in cyclopentasiloxane, such as that which is sold under the name        Q2-1401 by DOW CORNING,    -   the substituents R¹ to R⁶ are a methyl group, the substituent X        is a hydroxyl group, p=0 and n=2700, in a 13% strength solution        in dimethicone, such as that which is sold under the name        Q2-1403 by DOW CORNING,    -   the substituents R₁, R₂, R₅, R₆ and X are a methyl group, the        substituents R³ and R⁴ are an aryl group, and the molecular        weight of the compound is 600 000, such as that which is sold        under the name 761 by RHONE-POULENC.        (B4) Polyalkoxylated Silicones

Polyalkoxylated silicones (B4) are compounds which are chosen from thecompounds of the formulae:

where, in the formulae B-4a, B-4b, B-4c and B-4d

-   -   the groups R¹, which are identical or different from one        another, are a straight-chain or branched C₁ to C₃₀-alkyl group        or a phenyl group, in particular —CH₃    -   the groups R², which are identical or different from one        another, are R¹ or a group        —C_(c)H_(2c)—O—(C₂H₄O)_(a)(C₃H₆O)_(b)—R⁵ or a group        C_(c)H_(2c)—O—(C₄H₈O)_(a)—R⁵, with the proviso that at least one        of the radicals R² is a group    -   —C_(c)H_(2c)—O—(C₂H₄O)_(a)(C₃H₆O)_(b)—R⁵ or a group        C_(c)H_(2c)—O—(C₄H₈O)_(a)—R⁵,    -   the groups R³ and R⁴, which are identical or different from one        another, are a straight-chain or branched C₁ to C₁₂-alkyl group        and preferably methyl,    -   the groups R⁵, which are identical or different from one        another, are chosen from a hydrogen atom, a straight-chain or        branched alkyl group having 1 to 12 carbon atoms, a        straight-chain or branched alkoxy group having 1 to 6 carbon        atoms, a straight-chain or branched acyl group having 2 to 40        carbon atoms, —SO₃M, a C₁₋₆-aminoalkoxy group optionally        substituted on the amino group, a C₂₋₆-aminoacyl group        optionally substituted on the amino group, —NHCH₂CH₂COOM,        —N(CH₂CH₂COOM)₂, an aminoalkyl group optionally substituted on        the amino group and on the alkyl group, a C₂₋₃₀-carboxyacyl        group, a phosphono group optionally substituted by one or two        substituted aminoalkyl groups, —CO(CH₂)_(d)COOM,        —COCHR₇(CH₂)_(d)COOM, —NHCO(CH₂)_(d)OH, —NH₃Y or a phosphate        group,    -   the groups M, which are identical or different from one another,        are hydrogen, Na, K, Li, NH₄ or an organic amine,    -   R₇ is hydrogen or SO₃M,    -   d is in the range from 1 to 10,    -   m is in the range from 0 to 20,    -   n is in the range from 0 to 500,    -   o is in the range from 0 to 20,    -   p is in the range from 1 to 50,    -   a is in the range from 0 to 50,    -   b is in the range from 0 to 50,    -   a+b is at least 2,    -   c is in the range from 0 to 4,    -   x is in the range from 1 to 100, and    -   Y is a monovalent inorganic or organic anion,    -   with the proviso that n is greater than 12 if the silicone        corresponds to the formula B-4b where R₅=hydrogen.

The polyalkoxylated silicones according to the invention can likewise bechosen from the silicones of the following formula B-4e:([Z(R₂SiO)_(q)R′₂SiZO][(C_(n)H_(2n)O)_(r)])₅   (B-4e)in which:

-   -   R₂ and R′₂, which are identical or different, are a monovalent        hydrocarbon-containing radical,    -   n is an integer from 2 to 4,    -   q is a number of at least 4, preferably between 4 and 200 and in        particular between 4 and 100,    -   r is a number of at least 4, preferably between 4 and 200 and in        particular between 5 and 100,    -   s is a number of at least 4, preferably between 4 and 1000 and        in particular between 5 and 300,    -   Z is a divalent organic group which is bonded via a        carbon-silicon bond to the adjacent silicon atom and via an        oxygen atom to a polyoxyalkylene block,    -   the average molecular weight of each siloxane block is between        400 and about 10 000, that of each polyoxyalkylene block is        between about 300 and about 10 000,    -   the siloxane blocks are about 10 to about 95% by weight of the        block copolymer,    -   the number-average molecular weight of the block copolymer can        be between 2500 to 1 000 000 and preferably between 3000 ad 200        000 and in particular between 6000 and 100 000.

R₂ and R′₂ are preferably chosen from the group which comprises thestraight-chain or branched alkyl radicals, such as, for example, themethyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecylradicals, the aryl radicals, such as, for example, the phenyl, naphthylradicals, the aralkyl radicals or alkylaryl radicals, such as, forexample, the benzyl radicals, the phenylethyl radicals, the tolylradicals and the xylyl radicals.

Z is preferably —R″—, —R″—CO—, —R″—NHCO—, —R″—NH—CO—NH—R″—,—R′″—OCONH—R′″—NHCO—, where R″ is a divalent, straight-chain or branchedalkylene group having 1 to 6 carbon atoms, such as, for example,ethylene, propylene or butylene, straight-chain or branched, and R′″ isa divalent alkylene group or a divalent arylene group such as —C₆H₄—,—C₆H₄—C₆H₄—, —C₆H₄CH₂—C₆H₄—, —C₆H₄C(CH₃)₂C₆H₄—.

In a more preferred manner, Z is a divalent alkylene radical, inparticular the radical —C₃H₆ or the radical C₄H₈, straight-chain orbranched.

The preparation of the block copolymers used for the purposes of thisinvention is described in European application EP 0 492 657 A1, theteaching of which is included in this description.

Such products are marketed, for example, under the name SILICONFLUIDFZ-2172 by OSI.

The silicones according to the invention can be in the form of aqueoussolutions or optionally in the form of aqueous dispersions or emulsions.

Silicone-Containing Polyurethanes (B-5)

Further silicones which can be used are silicone-containingpolyurethanes. Of particular suitability are water-soluble orwater-disppersible polyurethanes derived from

-   a) at least one polysiloxane,-   b) at least one polyesterdiol,-   c) at least one compound with a molecular weight in the range from    56 to 300, which comprises two active hydrogen atoms per molecule,-   d) at least one compound which has two active hydrogen atoms and at    least one anionogenic or anionic group per molecule,-   e) at least one diisocyanate,    or the salts thereof, where the polyurethane comprises no unit which    originates from a primary or secondary amine which has an ionogenic    or ionic group.

Component a) is preferably a polymer with a number-average molecularweight in the range from about 400 to 4000, preferably 500 to 4000, inparticular 600 to 3000.

The polysiloxanes a) are preferably a compound of the formula B-5a

Iin which

-   R¹ and R², independently of one another, are C₁- to C₄-alkyl, benzyl    or phenyl,-   X and Y, independently of one another, are OH or NHR³, where R³ is    hydrogen, C₁- to C₆-alkyl or C₅- to C₈-cycloalkyl,-   m and n, independently of one another, are 2 to 8,-   p is 3 to 50.

Suitable alkyl radicals are, for example, methyl, ethyl, n-propyl,isopropyl, n-butyl, t-butyl, n-pentyl, n-hexyl etc. Suitable cycloalkylradicals are, for example, cyclopentyl, cyclohexyl, cycloheptyl,cyclooctyl etc.

Preferably, R¹ and R² are both methyl.

Polyesterdiols b) which can be used have a number-average molecularweight in the range from about 400 to 5000, preferably 500 to 3000, inparticular 600 to 2000.

Suitable polyesterdiols are all those which are usually used for thepreparation of polyurethanes, in particular those based on aromaticdicarboxylic acids, such as terephthalic acid, isophthalic acid,phthalic acid, Na or K sulfoisophthalic acid etc., aliphaticdicarboxylic acids, such as adipic acid or succinic acid etc., andcycloaliphatic dicarboxylic acids, such as 1,2-, 1,3- or1,4-cyclohexanedicarboxylic acid. Suitable diols are, in particular,aliphatic diols, such as ethylene glycol, propylene glycol,1,6-hexanediol, neopentyl glycol, diethylene glycol, polyethyleneglycols, polypropylene glycols, 1,4-dimethylolcyclohexane, andpoly(meth)acrylate-diols of the formula B-5b

in which R¹⁰ is H or CH₃ and R¹¹ is C₁-C₁₈-alkyl (in particular C₁-C₁₂-or C₁-C₈-alkyl), which have a molar mass of up to about 3000. Such diolscan be prepared in the usual manner and are commercially available(Tegomer™ grades MD, BD and OD from Goldschmidt).

Preference is given to polyesterdiols based on aromatic and aliphaticdicarboxylic acids and aliphatic diols, in particular those in which thearomatic dicarboxylic acid constitutes 10 to 95 mol %, in particular 40to 90 mol % and preferably 50 to 85 mol %, of the total dicarboxylicacid fraction (remainder is aliphatic dicarboxylic acids).

Particularly preferred polyesterdiols are the reaction products ofphthalic acid/diethylene glycol, isophthalic acid/1,4-butanediol,isophthalic acid/adipic acid/1,6-hexanediol, 5-NaSO₃-isophthalicacid/phthalic acid/adipic acid/1,6-hexanediol, adipic acid/ethyleneglycol, isophthalic acid/adipic acid/neopentyl glycol, isophthalicacid/adipic acid/neopentyl glycol/diethyleneglycol/dimethylolcyclohexane and 5-NaSO₃-isophthalic acid/isophthalicacid/adipic acid/neopentyl glycol/diethyleneglycol/dimethylolcyclohexane.

Component c) is preferably diols, diamines, aminoalcohols and mixturesthereof. The molecular weight of these compounds is preferably in arange from about 56 to 280. If desired, up to 3 mol % of said compoundsmay be replaced by triols or triamines. The resulting polyurethanes hereare essentially uncrosslinked.

As component c), preference is given to using diols. Diols which can beused are, for example, ethylene glycol, propylene glycol, butyleneglycol, neopentyl glycol, dimethylolcyclohexane, di-, tri-, tetra-,penta- or hexaethylene glycol and mixtures thereof. Preference is givento using neopentyl glycol and/or dimethylolcyclohexane.

Suitable aminoalcohols are, for example, 2-aminoethanol,2-(N-methylamino)ethanol, 3-aminopropanol, 4-aminobutanol,1-ethylaminobutan-2-ol, 2-amino-2-methyl-1-propanol,4-methyl-4-aminopentan-2-ol etc.

Suitable diamines are, for example, ethylenediamine, propylenediamine,1,4-diaminobutane, 1,5-diaminopentane and 1,6-diaminohexane, andα,ω-diaminopolyethers which can be prepared by amination of polyalkyleneoxides with ammonia.

Suitable compounds d) which have two active hydrogen atoms and at leastone ionogenic or anionic group per molecule are, for example, compoundswith carboxylate and/or sulfonate groups. As component d), particularpreference is given to dimethylolpropanoic acid and mixtures whichcomprise dimethylolpropanoic acid.

As component d), it is also possible to use compounds of the formulaeH₂N(CH₂)_(n)—NH—(CH₂)_(m)—COO⁻M⁺H₂N(CH₂)_(n)—NH—(CH₂)_(m)—SO₃ ⁻M⁺in which m and n, independently of one another, are an integer from 1 to8, in particular 1 to 6, and M is Li, Na or K. As component d),preference is given to using mixtures which have dimethylolpropanoicacid and up to 3% by weight, based on the total amount of components a)to e), of at least one compound of the abovmentioned formulae.

Component e) is customary aliphatic, cycloaliphatic and/or aromaticdiisocyanates, such as tetramethylene diisocyanate, hexamethylenediisocyanate, methylenediphenyl diisocyanate, 2,4- and 2,6-tolylenediisocyanate and isomeric mixtures thereof, 1,5-naphthylenediisocyanate, 1,4-cyclohexylene diisocyanate, dicyclohexylmethanediisocyanate and mixtures thereof, in particular isophorone diisocyanateand/or dicyclohexylmethane diisocyanate. If desired, up to 3 mol % ofsaid compounds may be replaced by triisocyanates.

Preferably, the silicon-containing polyurethanes (B-5) used arecompounds derived from

-   -   0.5 to 40% by weight, preferably 2 to 30% by weight, of at least        one polysiloxane a),    -   1 to 45% by weight, preferably 2 to 35% by weight, of at least        one polyester-diol b),    -   0.3 to 15% by weight, preferably 0.5 to 12% by weight, of at        least one component c),    -   5 to 25% by weight, preferably 8 to 20% by weight, of at least        one component d),    -   25 to 60% by weight, preferably 35 to 53% by weight, of at least        one component e).

Preferably, this is a silicon-containing polyurethane derived from

-   -   0.2 to 20% by weight, preferably 0.5 to 15% by weight, in        particular 1 to 10% by weight, of at least one polysiloxane a),    -   10 to 45% by weight, preferably 15 to 40% by weight, of at least        one polyester-diol b),    -   0.3 to 15% by weight, preferably 0.5 to 12% by weight, of at        least one component c),    -   5 to 25% by weight, preferably 8 to 20% by weight, of at least        one component d),    -   25 to 60% by weight, preferably 35 to 53% by weight, of at least        one component e).

The silicone-containing polyurethanes are prepared by reacting thecompounds of components a), b), c) and d) with the component e). Thetemperature here is in a range from about 60 to 140° C., preferablyabout 70 to 100° C. The reaction can be carried out without solvents orin a suitable inert solvent or solvent mixture. Suitable solvents areaprotic-polar solvents, e.g. tetrahydrofuran, ethyl acetate,N-methylpyrrolidone, di-methylformamide and preferably ketones, such asacetone and methyl ethyl ketone. Preferably, the reaction is carried outunder an inert gas atmosphere, such as, for example, under nitrogen. Thecomponents are used in amounts such that the ratio of NCO equivalent ofthe compounds of component e) to equivalent of active hydrogen atom ofcomponents a), b), c) and d) is in a range from about 0.8:1 to 1.25:1,preferably 0.85:1 to 1.2:1, in particular 1.05:1 to 1.15:1. If theresulting polyurethanes still have free isocyanate groups, these aresubsequently deactivated by adding amines, preferably aminoalcohols.Suitable aminoalcohols are those described above as component c),preferably 2-amino-2-methyl-1-propanol.

The polyurethanes comprising acid groups can be converted into awater-soluble or water-dispersible form by partial or completeneutralization with a base.

As a rule, the resulting salts of the polyurethanes have better watersolubility or dispersibility in water than the nonneutralizedpolyurethanes. Bases which can be used for the neutralization of thepolyurethanes may be alkali metal bases, such as sodium hydroxidesolution, potassium hydroxide solution, sodium carbonate, sodiumhydrogencarbonate, potassium carbonate or potassium hydrogencarbonateand alkaline earth metal bases, such as calcium hydroxide, calciumoxide, magnesium hydroxide or magnesium carbonate, and ammonia andamines. Suitable amines are, for example, C₁-C₆-alkylamines, preferablyn-propylamine and n-butylamine, dialkylamines, preferablydiethylpropylamine and dipropylmethylamine, trialkylamines, preferablytriethylamine and triisopropylamine, C₁-C₆-alkyldiethanolamines,preferably methyl- or ethyldiethanolamine anddi-C₁-C₆-alkylethanolamines. For use in hair-treatment compositions inparticular, 2-amino-2-methyl-1-propanol, diethylaminopropylamine andtriisopropanolamine have proven successful for the neutralization of thepolyurethanes comprising acid groups. The neutralization of thepolyurethanes comprising acid groups can also be undertaken usingmixtures of two or more bases, e.g. mixtures of sodium hydroxide andtriisopropanolamine. The neutralization can be carried out partially,e.g. to 20 to 40%, or completely, i.e. to 100%, depending on theintended use.

If, in the preparation of the polyurethanes, a water-miscible organicsolvent is used, then this can be removed subsequently by customarymethods known to the person skilled in the art, e.g. by distillation atreduced pressure. Before separating off the solvent, water canadditionally be added to the polyurethane. Replacing the solvent withwater gives a solution or dispersion of the polymer from which, ifdesired, the polymer can be obtained in the customary manner, e.g. byspray drying.

The silicone-containing polyurethanes (B-5) have K values (measured inaccordance with E. Fikentscher, Cellulose-Chemie 13 (1932), pp. 58-64,on a 1% strength solution in N-methylpyrrolidone) in a range from 15 to90, preferably 20 to 60. Their glass transition temperature is generallyat least 0° C., preferably at least 20° C., especially preferably atleast 25° C. and specifically at least 30° C.

If the silicone-containing polyurethanes (B-5) used are polyurethaneswith units derived from polysiloxanes of the formula B-5a, then theproportion of siloxane groups, based on the solids content of thesilicone-containing polyurethanes, is generally about 0.05 to 20% byweight, preferably about 0.05 to 15% by weight, in particular 0.05 to10% by weight.

Particularly preferred silicones are polyalkoxylated silicones (B-4).

The present invention further provides a process for the preparation ofpolymeric products, which comprises

-   -   i) polymerizing ethylenically unsaturated monomers (A-1) in the        presence of unsaturated polyalkylene glycol vinyl ethers (A-2)    -   ii) mixing the resulting polymer with silicones at a temperature        greater than or equal to 30° C.        i) Preparation of Polymers (A)

The polymers (A) can be prepared by customary conventional syntheticmethods of polymerization. For example, these may be solutionpolymerization, emulsion polymerization, inverse emulsionpolymerization, suspension polymerization, inverse suspensionpolymerization or precipitation polymerization, without the methodswhich can be used being limited thereto. In solution polymerization,water, customary organic solvents or the unsaturated polyalkylene glycolvinyl ethers (A-2) can themselves be used as solvents.

The regulators which may be used are the customary compounds known tothe person skilled in the art, such as, for example, sulfur compounds(e.g.: mercaptoethanol, 2-ethylhexyl thioglycolate, thioglycolic acid ordodecyl mercaptan), and tribromochloromethane and other compounds whichhave a regulating effect on the molecular weight of the resultingpolymers. It is also possible in some instances to use thiolgroup-containing silicone compounds. Preference is given to usingsilicone-free regulators.

In one embodiment of the invention, additional crosslinking monomers areused in the preparation of the polymers (A). Crosslinking monomers whichmay be used are compounds with at least two ethylenically unsaturateddouble bonds, such as, for example, esters of ethylenically unsaturatedcarboxylic acids, such as acrylic acid or methacrylic acid, andpolyhydric alcohols, ethers of at least dihydric alcohols, such as, forexample, vinyl ether or allyl ether. Also suitable are straight-chain orbranched, linear or cyclic aliphatic or aromatic or aromatichydrocarbons which have at least two double bonds, which in the case ofthe aliphatic hydrocarbons must not be conjugated. Also suitable areamides of acrylic acid and methacrylic acid and N-allylamines of atleast difunctional amines, such as, for example, 1,2-diaminoethane,1,3-diaminopropane. Also are triallylamine or corresponding ammoniumsalts, N-vinyl compounds of urea derivatives, at least difunctionalamides, cyanurates or urethanes. Further suitable crosslinkers aredivinyldioxane, tetraallylsilane or tetravinylsilane.

Particularly preferred crosslinkers are, for example,methylenebisacrylamide, triallylamine and triallylammonium salts,divinylimidazole, N,N′-divinylethyleneurea, reaction products ofpolyhydric alcohols with acrylic acid or methacrylic acid, methacrylicesters and acrylic esters of polyalkylene oxides or polyhydric alcoholswhich have been reacted with ethylene oxide and/or propylene oxideand/or epichlorohydrin.

The monomers (A-1) according to the invention can, if they compriseionizable groups, be neutralized partially or completely with acids orbases before or after the polymerization in order, for example, toadjust the solubility or dispersibility in water to a desired extent.

Neutralizing agents for monomers carrying acid groups which can be usedare, for example, mineral bases, such as sodium carbonate, alkali metalhydroxides and ammonia, organic bases, such as aminoalcohols,specifically 2-amino-2-methyl-1-propanol, monoethanolamine,diethanolamine, triethanolamine, triisopropanolamine,tri[(2-hydroxy)-1-propyl]amine, 2-amino-2-methyl-1,3-propanediol,2-amino-2-hydroxymethyl-1,3-propanediol, and diamines, such as, forexample, lysine.

Neutralizing agents which can be used for monomers carrying cationizablegroups may, for example, be mineral acids, such as hydrochloric acid,sulfuric acid or phosphoric acid, and organic acids, such as carboxylicacids, lactic acid, citric acid or others.

The monomers (A-1 ) of the polymers (A) can constitute from 50 to 99.9%by weight, preferably 70 to 99% by weight, particularly preferably 85 to98% by weight, in particular 80 to 97% by weight.

The monomers (A-2, unsaturated polyalkylene glycol vinyl ethers) aregenerally present in the polymer (A) in amounts of from 0.1 to 50,preferably from 0.5 to 20, particularly preferably from 2 to 15, % byweight.

In a preferred embodiment of the invention, the monomers (A-1) used areat least 2 monomers (a1 and a2). Particular preference is given topolymers (A) which are obtainable by polymerization of monomer (a1)tert-butyl acrylate and monomer (a2) methacrylic acid. If theethylenically unsaturated monomers (A-1) are used as a combination oftwo monomers (a1 and a2), it has proven advantageous to use 49.5 to 99%by weight of (a1) and 0.5 to 40% by weight of (a2).

In a particularly preferred embodiment, the polymer (A) used is apolymer which is obtainable by free-radical polymerization of a monomermixture of

-   -   (a1) 49.5 to 99% by weight of (meth)acrylate, in particular        tert-butyl acrylate    -   (a2) 0.5 to 40% by weight of a further (meth)acrylate, in        particular methacrylic acid    -   (b) 0.5 to 20% by weight of an unsaturated polyalkylene glycol        ether (A-2)

In a particularly preferred embodiment, the polymer (A) used is apolymer which is obtainable by free-radical polymerization of a monomermixture of

-   -   (a1) 49.5 to 99% by weight of (meth)acrylate, in particular        tert-butyl acrylate    -   (a2) 0.5 to 40% by weight of a further (meth)acrylate, in        particular methacrylic acid    -   (c) 0.5 to 20% by weight of an unsaturated polyalkylene glycol        ether (A-2) of the following formula        H₂C═CH—C_(c)H_(2c)—O—(C₂H₄O)_(a)(C₃H₆O)_(b)—R⁵    -   where R⁵═H, CH₃,    -   a is in the range from 0 to 50,    -   b is in the range from 0 to 50,    -   a+b is greater than 0,    -   c is 0, 1, 2, 3 or 4.

The polymers (A) preferably have a K value (measured according toFickentscher, Cellulosechemie, vol. 13, pp. 58-64 (1932) at 250° C. 0.15% strength in 0.5 molar sodium chloride solution) of from 30 to 50,preferably from 37 to 41.

Particularly suitable polymers (A) are those which are water-soluble orwhose dispersibility in water is so great that they are soluble in asolvent mixture of water:ethanol=20:80 (% by volume:% by volume) in anamount of more than 0.1 g/l, preferably more than 0.2 g/l.

For the purposes of the invention, water-dispersible polymers meanspolymers which, upon contact with water, within 24 hours form a fluidwhich does not allow any solid particles to be detected by the eyewithout optical devices. To check whether a polymer is dispersible inwater, 100 mg of the polymer in the form of a 100 mm thick film areplaced in 100 ml of water (20° C.) and shaken for 24 hours on acommercially available shaking table. If, after the shaking, solidparticles can no longer be seen, but the fluid possesses turbidity, thepolymer is water-dispersible; without turbidity, it is referred to aswater-soluble.

In the polymerization of the monomers (A-1) and (A-2), it is optionallypossible for other polymers, such as, for example, homopolymers andcopolymers of ethylenically unsaturated monomers, and also polyamides,polyurethanes or polyesters, to also be present. The polyamides,polyurethanes, polyesters are preferably ionically modified, e.g. withcarboxylate or sulfonate groups.

ii) Mixing of Polymers (A) with Silicones (B)

The polymeric products according to the invention are obtainable in thesimplest case by mixing the components (A) and (B). It is essentialaccording to the invention that the temperature during mixing is greaterthan or equal to 30° C., in particular greater than or equal to 40° C.

In a particularly preferred embodiment of the invention, the polymericproducts according to the invention are prepared by mixing (A) and (B)at temperatures greater than or equal to 50° C., in particular greaterthan or equal to 60° C., particularly preferably greater than or equalto 70° C.

It has proven advantageous to carry out the mixing for at least 30minutes, in particular for at least 60 minutes.

For the mixing, all apparatuses known to a person skilled in the art aresuitable. The mixing can be carried out with inert-gas gassing, e.g.nitrogen gassing.

In a preferred embodiment, 99.5 to 70% by weight, in particular 99 to85% by weight, of (A) and 0.5 to 30% by weight, in particular 1 to 15%,by weight of (B), are used.

The polymeric products according to the invention are suitable inparticular for use in cosmetic preparations, particularly in haircosmetic preparations.

The present invention therefore further provides for the use of thepolymeric products in cosmetic preparations.

For example, the polymeric products according to the invention are usedin cosmetic compositions for cleansing the skin. Such cosmetic cleansingcompositions are chosen from bar soaps, such as toilet soaps, curdsoaps, transparent soaps, luxury soaps, deodorant soaps, cream soaps,baby soaps, skin protection soaps, abrasive soaps and syndets, liquidsoaps, such as pasty soaps, lubricating soaps and washing pastes, andliquid washing, showering and bathing preparations, such as washinglotions, shower baths and gels, foam baths, oil baths and scrubpreparations.

Preferably, the polymeric products according to the invention are usedin cosmetic compositions for the care and protection of the skin, innailcare compositions, and in preparations for decorative cosmetics.

Particular preference is given to the use in skincare compositions,intimate care compositions, footcare compositions, deodorants, lightprotection compositions, repellents, shaving compositions, hair removalcompositions, antiacne compositions, make-up, mascara, lipsticks,eyeshadows, kohl pencils, eyeliners, blushers, powders and eyebrowpencils.

The skincare compositions are, in particular, in the form of W/O or O/Mskin creams, day creams and night creams, eye creams, face creams,antiwrinkle creams, moisturizing creams, bleaching creams, vitamincreams, skin lotions, care lotions and moisturizing lotions.

In the cosmetic preparations, the polymeric products according to theinvention can develop particular effects. They can, inter alia,contribute to the moisturization and conditioning of the skin and to theimprovement in the feel of the skin. By adding the polymeric productsaccording to the invention, it is possible, in certain formulations, toachieve a considerable improvement in the skin compatibility.

The polymeric products according to the invention are present in theskin cosmetic preparations in an amount of from about 0.001 to 20% byweight, preferably from 0.01 to 10% by weight, very particularlypreferably from 0.1 to 5% by weight, based on the total weight of thecomposition.

Depending on the field of use, the compositions according to theinvention can be applied in a form suitable for skincare, such as, forexample, in the form of a cream, foam, gel, pencil, powder, mousse, milkor lotion.

In addition to the dispersions according to the invention and suitablesolvents, the skin cosmetic preparations may also comprise additivescustomary in cosmetics, such as emulsifiers, preservatives, perfumeoils, cosmetic active ingredients, such as phytantriol, vitamin A, E andC, retinol, bisabolol, panthenol, light protection agents, bleaches,colorants, tinting agents, tanning agents (e.g. dihydroxyacetone),collagen, protein hydrolysates, stabilizers, pH regulators, dyes, salts,thickeners, gelling agents, consistency-imparting agents, silicones,humectants, refatting agents and further customary additives.

Suitabe solvents are, in particular, water and lower monoalcohols orpolyols having 1 to 6 carbon atoms or mixtures thereof; preferredmonoalcohols or polyols are ethanol, isopropanol, propylene glycol,glycerol and sorbitol.

Further customary additives which may be present are fatty substances,such as mineral and synthetic oils, such as, for example, paraffins,silicone oils and aliphatic hydrocarbons with more than 8 carbon atoms,animal and vegetable oils, such as, for example, sunflower oil, coconutoil, avocado oil, olive oil, lanolin, or waxes, fatty acids, fatty acidesters, such as, for example, triglycerides of C₆-C₃₀-fatty acids, waxesters, such as, for example, jojoba oil, fatty alcohols, petroleumjelly, hydrogenated lanolin and acetylated lanolin. It is of course alsopossible to use mixtures thereof.

Customary thickeners in such formulations are crosslinked polyacrylicacids and derivatives thereof, polysaccharides, such as xanthan gum,agar agar, alginates or Tyloses, carboxymethylcellulose orhydroxycarboxymethylcellulose, fatty alcohols, monoglycerides and fattyacids, polyvinyl alcohol and polyvinylpyrrolidone.

The polymeric products according to the invention can be mixed withconventional polymers if specific properties are to be set.

Suitable conventional polymers are, for example, anionic, cationic,amphoteric and neutral polymers.

Examples of anionic polymers are homopolymers and copolymers of acrylicacid and methacrylic acid or salts thereof, copolymers of acrylic acidand acrylamide and salts thereof; sodium salts of polyhydroxycarboxylicacids, water-soluble or water-dispersible polyesters, polyurethanes andpolyureas. Particularly suitable polymers are copolymers of t-butylacrylate, ethyl acrylate, methacrylic acid (e.g. Luvimer™ 100P),copolymers of ethyl acrylate and methacrylic acid (e.g. Luvimer™ MAE),copolymers of N-tert-butylacrylamide, ethyl acrylate, acrylic acid(Ultrahold™ 8, strong), copolymers of vinyl acetate, crotonic acid andoptionally further vinyl esters (e.g. Luviset™ grades), maleic anhydridecopolymers, optionally reacted with alcohols, anionic polysiloxanes,e.g. carboxyfunctional ones, copolymers of vinylpyrrolidone, t-butylacrylate, methacrylic acid (e.g Luviskol™ VBM), copolymers of acrylicacid and methacrylic acid with hydrophobic monomers, such as, forexample, C₄-C₃₀-alkyl esters of meth(acrylic acid), C₄-C₃₀-alkyl vinylesters, C₄-C₃₀-alkyl vinyl ethers and hyaluronic acid, Luviset P.U.R.,Luviflex™ Silk.

Further suitable polymers are cationic polymers with the INCI namePolyquaternium, e.g. copolymers of vinylpyrrolidone/N-vinylimidazoliumsalts (Luviquat™ FC, Luviquat™ HM, Luviquat™ MS, Luviquat™ Care,Luviquat™ Hold, INCl Polyquaternium-16, -44, -46), copolymers ofacrylamide and dimethyldiallylammonium chloride (Polyquaternium-7),cationic cellulose derivatives (Polyquaternium-4, -10), cationic starchderivatives (INCl: Starch Hydroxypropytrimonium Chloride, Corn StarchModified), cationic guar derivatives (INCl: Hydroxypropyl GuarHydroxypropyltrimonium Chloride), cationic sunflower oil derivatives(INCl: Sunflowerseedamidopropyl Hydroxyethyldimonium Chloride),copolymers of N-vinypyrrolidone/dimethylaminoethyl methacrylate,quaternized with diethyl sulfate (Polyquaternium-11), copolymers ofacrylic acid, acrylamide and methacrylamidopropyltrimonium chloride(Polyquaternium-53), Polyquaternium-32, Polyquaternium-28 and others.

Suitable further polymers are also neutral polymers, such aspolyvinylpyrrolidones, copolymers of N-vinylpyrrolidone and vinylacetate and/or vinyl propionate, copolymers ofN-vinypyrrolidone/dimethylaminopropylacrylamide or -methacrylamide,copolymers of N-vinylpyrrolidone and alkyl acrylate or methacrylatemonomers with alkyl chains from C1 to C18, graft copolymers of polyvinylalcohol onto polyalkylene glycols, such as, for example, Kollicoat IR(BASF), graft copolymers of other vinyl monomers onto polyalkyleneglycols, polysiloxanes, polyvinylcaprolactam and copolymers containingN-vinylpyrrolidone, polyethylenimines and salts thereof, polyvinylaminesand salts thereof, cellulose derivatives, chitosan, polyaspartic acidsalts and derivatives.

To set certain properties, the preparations can additionally alsocomprise conditioning substances based on silicone compounds. Suitablesilicone compounds are, for example, polyalkylsiloxanes,polyarylsiloxanes, polyarylalkylsiloxanes, polyethersiloxanes, siliconeresins, dimethicones, dimethicone derivatives or dimethicone copolyols(CTFA) and aminofunctional silicone compounds, such as amodimethicones(CTFA).

The polymeric products according to the invention are used in cosmeticpreparations whose preparation takes place in accordance with thecustomary guidelines familiar to the person skilled in the art.

Such formulations are advantageously in the form of emulsions,preferably in the form of water-in-oil (W/O) or oil-in-water (O/W)emulsions. It is, however, also possible according to the invention andin some cases advantageous to choose other types of formulation, forexample hydrodispersions, gels, oils, oleogels, multiple emulsions, forexample in the form of W/O/W or O/W/O emulsions, anhydrous ointments orointment bases etc.

The preparation of emulsions which can be used according to theinvention takes place in accordance with known methods.

In addition to the polymeric products according to the invention, theemulsions comprise customary constituents, such as fatty alcohols, fattyacid esters and in particular fatty acid triglycerides, fatty acids,lanolin and derivatives thereof, natural or synthetic oils or waxes andemulsifiers in the presence of water.

The choice of additives specific to the type of emulsion and thepreparation of suitable emulsions is described, for example, inSchrader, Grundlagen und Rezepturen der Kosmetika [Fundamentals andformulations of cosmetics], Hüthig Buch Verlag, Heidelberg, 2nd edition,1989, third part, which is hereby expressly incorporated by reference.

Thus, a skin cream which can be used according to the invention may, forexample, be in the form of a W/O emulsion. Such an emulsion comprises anaqueous phase which is emulsified in an oil or fatty phase using asuitable emulsifier system.

The concentration of the emulsifier system in this type of emulsion isabout 4 and 35% by weight, based on the total weight of the emulsion;the fatty phase constitutes about 20 and 60% by weight and the aqueousphases about 20 and 70% by weight, in each case based on the totalweight of the emulsion. The emulsifiers are those which are customarilyused in this type of emulsion. They are chosen, for example, from:C₁₂-Cl₁₈-sorbitan fatty acid esters; esters of hydroxystearic acid andC12-C₃₀-fatty alcohols; monoesters and diesters of C₁₂-C₁₈-fatty acidsand glycerol or polyglycerol; condensates of ethylene oxide andpropylene glycols; oxypropylenated/oxyethylenated C₁₂-C₂₀-fattyalcohols; polycyclic alcohols, such as sterols; aliphatic alcohols witha high molecular weight, such as lanolin; mixtures ofoxypropylenated/polyglycerolated alcohols and magnesium isostearate;succinic esters of polyoxyethylenated or polyoxypropylenated fattyalcohols; and mixtures of magnesium, calcium, lithium, zinc or aluminumlanolate and hydrogenated lanolin or lanolin alcohol.

Suitable fatty components which may be present in the fatty phase of theemulsions include hydrocarbon oils, such as paraffin oil, purcellin oil,perhydrosqualene and solutions of microcrystalline waxes in these oils;animal or vegetable oils, such as sweet almond oil, avocado oil,calophylum oil, lanolin and derivatives thereof, castor oil, sesame oil,olive oil, jojoba oil, karité oil, hoplostethus oil; mineral oils whosedistillation start-point under atmospheric pressure is at about 250° C.and whose distillation end-point is at 410° C., such as, for example,vaseline oil; esters of saturated or unsaturated fatty acids, such asalkyl myristates, e.g. isopropyl, butyl or cetyl myristate, hexadecylstearate, ethyl or isopropyl palmitate, octanoic or decanoictriglycerides and cetyl ricinoleate.

The fatty phase can also comprise silicone oils soluble in other oils,such as dimethylpolysiloxane, methylphenylpolysiloxane and the siliconeglycol copolymer, fatty acids and fatty alcohols.

In order to promote the retention of oils, it is also possible to usewaxes, such as, for example, carnauba wax, candellila wax, beeswax,microcrystalline wax, ozokerite wax and Ca, Mg and Al oleates,myristates, linoleates and stearates.

In general, these water-in-oil emulsions are prepared by introducing thefatty phase and the emulsifier into the batch container. This is heatedat a temperature of from 70 to 75° C., then the oil-soluble ingredientsare added and, with stirring, water which has been heated beforehand tothe same temperature and in which the water-soluble ingredients havebeen dissolved beforehand is added; the mixture is stirred until anemulsion of the desired fineness is achieved, which is then left to coolto room temperature, if necessary with a lesser amount of stirring.

In addition, a care emulsion according to the invention can be in theform of an O/W emulsion. Such an emulsion usually comprises an oilphase, emulsifiers which stabilize the oil phase in the water phase, andan aqueous phase, which is usually present in thickened form.

The aqueous phase of the O/W emulsion of the preparations according tothe invention optionally comprises

-   -   alcohols, diols or polyols, and ethers thereof, preferably        ethanol, isopropanol, propylene glycol, glycerol, ethylene        glycol monoethyl ether;    -   customary thickeners or gel formers, such as, for example,        crosslinked polyacrylic acids and derivatives thereof,        polysaccharides, such as xanthan gum or alginates,        carboxymethylcellulose or hydroxycarboxymethylcellulose, fatty        alcohols, polyvinyl alcohol and polyvinylpyrrolidone.

The oil phase comprises oil components customary in cosmetics, such as,for example:

-   -   esters of saturated and/or unsaturated, branched and/or        unbranched C₃-C₃₀-alkanecarboxylic acids and saturated and/or        unsaturated, branched and/or unbranched C₃-C₃₀-alcohols, of        aromatic carboxylic acids and saturated and/or unsaturated,        branched and/or unbranched C₃-C₃₀-alcohols, for example        isopropyl myristate, isopropyl stearate, hexyldecyl stearate,        oleyl oleate; and also synthetic, semisynthetic and natural        mixtures of such esters, such as jojoba oil;    -   branched and/or unbranched hydrocarbons and hydrocarbon waxes;    -   silicone oils, such as cyclomethicone, dimethylpolysiloxane,        diethylpolysiloxane, octamethylcyclotetrasiloxane and mixtures        thereof;    -   dialkyl ethers;    -   mineral oils and mineral waxes;    -   triglycerides of saturated and/or unsaturated, branched and/or        unbranched C₈-C₂₄-alkanecarboxylic acids; they can be chosen        from synthetic, semisynthetic or natural oils, such as olive        oil, palm oil, almond oil or mixtures.

Suitable emulsifiers are preferably O/W emulsifiers, such aspolyglycerol esters, sorbitan esters or partially esterified glycerides.

The preparation can also take place by melting the oil phase at about80° C.; the water-soluble constituents are dissolved in hot water, andadded to the oil phase slowly and with stirring; the mixture ishomogenized and stirred until cold.

The polymeric products according to the invention are also suitable foruse in washing and shower gel formulations, and bathing preparations.

As well as the polymeric products according to the invention, suchformulations usually comprise anionic surfactants as base surfactantsand amphoteric and nonionic surfactants as cosurfactants, and alsolipids, perfume oils, dyes, organic acids, preservatives andantioxidants, and also thickeners/gel formers, skin conditioners andhumectants.

In the washing, showering and bathing preparations, all anionic,neutral, amphoteric or cationic surfactants customarily used inbody-cleansing compositions may be used.

The formulations comprise 2 to 50% by weight of surfactants, preferably5 to 40% by weight, particularly preferably 8 to 30% by weight.

Suitable anionic surfactants are, for example, alkyl sulfates, alkylether sulfates, alkylsulfonates, alkylarylsulfonates, alkyl succinates,alkyl sulfosuccinates, N-alkoyl sarcosinates, alkylglycol alkoxylates,acyl taurates, acyl isethionates, alkyl phosphates, alkyl etherphosphates, alkyl ether carboxylates, alpha-olefinsulfonates, inparticular the alkali metal and alkaline earth metal salts, e.g. sodium,potassium, magnesium, calcium, and ammonium and triethanolamine salts.The alkyl ether sulfates, alkyl ether phosphates and alkyl ethercarboxylates can have between 1 and 10 ethylene oxide or propylene oxideunits, preferably 1 to 3 ethylene oxide units, in the molecule.

Suitable are, for example, sodium lauryl sulfate, ammonium laurylsulfate, sodium lauryl ether sulfate, ammonium lauryl ether sulfate,sodium lauryl sarcosinate, sodium oleyl succinate, ammonium laurylsulfosuccinate, sodium dodecylbenzenesulfonate, triethanolaminedodecylbenzenesulfonate.

Suitable amphoteric surfactants are, for example, alkylbetaines,alkylamidopropylbetaines, alkylsulfobetaines, alkyl glycinates, alkylcarboxyglycinates, alkyl amphoacetates or amphopropionates, alkylamphodiacetates or amphodipropionates.

For example, it is possible to use cocodimethylsulfopropylbetaine,laurylbetaine, cocamidopropylbetaine or sodium cocamphopropionate.

Suitable nonionic surfactants are, for example, the reaction products ofaliphatic alcohols or alkylphenols having 6 to 20 carbon atoms in thealkyl chain, which may be linear or branched, containing ethylene oxideand/or propylene oxide. The amount of alkylene oxide is about 6 to 60mols per mole of alcohol. In addition, alkylamine oxides, mono- ordialkylalkanolamides, fatty acid esters of polyethylene glycols,ethoxylated fatty acid amides, alkyl polyglycosides or sorbitan etheresters are suitable.

In addition, the washing, showering and bathing preparations cancomprise customary cationic surfactants, such as, for example,quaternary ammonium compounds, for example cetyltrimethylammoniumchloride or bromide (INCl Cetrimonium chloride or bromide),hydroxyethylcetyldimonium phosphate (INCl Quaternium-44), INClCocotrimonium methosulfate, INCl Quaternium-52.

In addition, further customary cationic polymers can also be used, suchas, for example, copolymers of acrylamide and dimethyldiallylammoniumchloride (Polyquaternium-7), cationic cellulose derivatives(polyquaternium-4, -10), cationic starch derivatives (INCl: StarchHydroxypropytrimonium Chloride, Corn Starch Modified), cationic guarderivatives (INCl: Hydroxypropyl Guar Hydroxypropyltrimonium Chloride),cationic sunflower oil derivatives (INCl: SunflowerseedamidopropylHydroxyethyldimonium Chloride), copolymers of N-vinylpyrrolidone andquaternized N-vinylimidazole (Polyquaternium-16, -44, -46), copolymersof N-vinypyrrolidone/dimethylaminoethyl methacrylate, quaternized withdiethyl sulfate (Polyquaternium-11), copolymers of acrylic acid,acrylamide and methacrylamidopropyltrimonium chloride(Polyquaternium-53), Polyquaternium-32, Polyquaternium-28 and others.

In addition, the washing and shower gel formulations and bathingpreparations can comprise thickeners, such as, for example, sodiumchloride, PEG-55, propylene glycol oleate, PEG-120 methyl glucosedioleate and others, and also preservatives, further active ingredientsand auxiliaries and water.

In a preferred embodiment of the invention, the polymeric products areused in hair cosmetic preparations.

Hair cosmetic preparations include, in particular, styling compositionsand/or conditioning compositions in hair cosmetic preparations such ashair treatments, hair mousses, (hair) gels or hair sprays, hair lotions,hair rinses, hair shampoos, hair emulsions, split end fluids,neutralizing agents for permanent waves, hair colorants and bleaches,hot-oil treatment preparations, conditioners, setting lotions or hairsprays. Depending on the field of use, the hair cosmetic preparationscan be applied in the form of an (aerosol) spray, (aerosol) mousse, gel,gel spray, cream, lotion or wax.

In a preferred embodiment, the hair cosmetic formulations according tothe invention comprise

a) 0.05 to 20% by weight of the polymeric product

b) 20 to 99.95% by weight of water and/or alcohol

c) 0 to 79.5% by weight of further constituents

Alcohol is understood as meaning all alcohols customary in cosmetics,e.g. ethanol, isopropanol, n-propanol.

Further constituents are understood as meaning additives customary incosmetics, for example propellants, antifoams, interface-activecompounds, i.e. surfactants, emulsifiers, foam formers and solubilizers.The interface-active compounds used may be anionic, cationic, amphotericor neutral. Further customary constituents may also be, for example,preservatives, perfume oils, emollients, effect substances, opacifiers,active ingredients, antioxidants, peroxide decomposers, UV filters, caresubstances such as panthenol, collagen, vitamins, protein hydrolysates,alpha- and beta-hydroxycarboxylic acids, protein hydrolysates,stabilizers, pH regulators, dyes, pigments, viscosity regulators, gelformers, salts, humectants, refatting agents, complexing agents andfurther customary additives.

These also include all styling and conditioning polymers known incosmetics which may be used in combination with the polymers accordingto the invention if very particular properties are to be set.

Suitable conventional hair cosmetic polymers are, for example, anionicpolymers. Such anionic polymers are homopolymers and copolymers ofacrylic acid and methacrylic acid or salts thereof, copolymers ofacrylic acid and acrylamide and salts thereof; sodium salts ofpolyhydroxycarboxylic acids, water-soluble or water-dispersiblepolyesters, polyurethanes (Luviset™ P.U.R.) and polyureas. Particularlysuitable polymers are copolymers of t-butyl acrylate, ethyl acrylate,methacrylic acid (e.g. Luvimer™ 100P), copolymers ofN-tert-butylacrylamide, ethyl acrylate, acrylic acid (e.g. Ultrahold™ 8,Strong), copolymers of vinyl acetate, crotonic acid and optionallyfurther vinyl esters (e.g. Luviset™ grades, INCl: VA/CrotonatesCopolymer), maleic anhydride copolymers, optionally reacted withalcohols, anionic polysiloxanes, e.g. carboxyfunctional ones, copolymersof vinylpyrrolidone, t-butyl acrylate, methacrylic acid (e.g Luviskol™VBM).

In addition, the group of polymers suitable for combination with thepolymeric products according to the invention includes, for example,Balance CR or 0/55 (National Starch; acrylate copolymer), Balance 47(National Starch; octylacrylamide/acrylate/butylaminoethyl methacrylatecopolymer), Aquaflex™ FX 64 (ISP;isobutylene/ethylmaleimide/hydroxyethylmaleimide copolymer), Aquaflex™SF-40 (ISP/National Starch; VP/vinyl caprolactam/DMAPA acrylatcopolymer), Allianz™ LT-120 (ISP/Rohm & Haas; acrylate/C1-2succinate/hydroxyacrylate copolymer), Aquarez™ HS (Eastman;polyester-1), Diaformer™ Z-400 (Clariant;methacryloylethylbetaine/methacrylate copolymer), Diaformer™ Z-711 orZ-712 (Clariant; methacryloylethyl N-oxide/methacrylate copolymer),Omnirez™ 2000 (ISP; monoethyl ester of poly(methyl vinyl ether/maleicacid in ethanol), Amphomer™ HC or Resyn XP or Resyn 28-4961 (NationalStarch; acrylate/octylacrylamide copolymer), Amphomer™ 28-4910 (NationalStarch; octylacrylamide/acrylate/butylaminoethyl methacrylatecopolymer), Advantage™ HC 37 (ISP; terpolymer ofvinylcaprolactam/vinylpyrrolidone/dimethylaminoethyl methacrylate),Advantage grades (ISP), Acudyne 258 (Rohm & Haas; acrylate/hydroxy esteracrylate copolymer), Luviset™ P.U.R. (BASF, polyurethane-1), Luviflex™Silk (BASF, PEG/PPG-25/25 dimethicone/acrylates copolymer), Eastman™AQ48 (Eastman), Styleze 2000 (ISP; VP/acrylates/lauryl methacrylatecopolymer), Styleze CC-10 (ISP; VP/DMAPA acrylates copolymer), StylezeW-20 (ISP), Fixomer A-30 (Ondeo Nalco; methacrylic acid/sodiumacrylamidomethylpropanesulfonate copolymer), Fixate G-100 (Noveon;AMP-acrylates/allyl methacrylate copolymer).

Very particularly preferred anionic polymers are acrylates with an acidnumber greater than or equal to 120 and copolymers of t-butyl acrylate,ethyl acrylate, methacrylic acid.

Further suitable hair cosmetic polymers are cationic polymers with theINCl name Polyquaternium, e.g. copolymers ofvinylpyrrolidone/N-vinylimidazolium salts (Luviquat™ FC, Luviquat™ HM,Luviquat™ MS, Luviquat™ Care, INCl: Polyquaternium-16,Polyquaternium-44), copolymers of N-vinylpyrrolidone/dimethylaminoethylmethacrylate, quaternized with diethyl sulfate (Luviquat™ PQ 11, INCl:Polyquaternium-11), copolymers ofN-vinylcaprolactam/N-vinylpyrrolidone/N-vinylimidazolium salts(Luviquat™ Hold, INCl: Polyquaternium-46); copolymers of acrylamide anddimethyldiallylammonium chloride (Polyquaternium-7), cationic cellulosederivatives (Polyquaternium-4, -10), cationic starch derivatives (INCl:Starch Hydroxypropytrimonium Chloride, Corn Starch Modified), cationicguar derivatives (INCl: Hydroxypropyl Guar HydroxypropyltrimoniumChloride), cationic sunflower oil derivatives (INCl:Sunflowerseedamidopropyl Hydroxyethyldimonium Chloride), copolymers ofacrylic acid, acrylamide and methacrylamidopropyltrimonium chloride(INCl: Polyquaternium-53), Polyquaternium-32, Polyquaternium-28 andothers.

Further suitable hair cosmetic polymers are also neutral polymers, suchas polyvinylpyrrolidones, copolymers of N-vinylpyrrolidone and vinylacetate and/or vinyl propionate, copolymers ofN-vinylpyrrolidone/dimethylaminopropylacrylamide or -methacrylamide,copolymers of N-vinylpyrrolidone and alkyl acrylate or methacrylatemonomers with alkyl chains from C1 to C18, graft copolymers of polyvinylalcohol onto polyalkylene glycols, such as, for example, Kollicoat IR(BASF), graft copolymers of other vinyl monomers onto polyalkyleneglycols, polysiloxanes, polyvinylcaprolactam and copolymers containingN-vinylpyrrolidone, polyethylenimines and salts thereof, polyvinylaminesand salts thereof, cellulose derivatives, chitosan, polyaspartic acidsalts and derivatives.

To set certain properties, the preparations can additionally alsocomprise conditioning substances based on silicone compounds. Suitablesilicone compounds are, for example, polyalkylsiloxanes,polyarylsiloxanes, polyarylalkylsiloxanes, polyethersiloxanes, siliconeresins, fluorinated alkylsilicones, dimethicones, dimethiconederivatives or dimethicone copolyols (CTFA) and aminofunctional siliconecompounds, such as amodimethicones (CTFA).

The polymers according to the invention are particularly suitable assetting agents in hairstyling preparations, in particular hair sprays(aerosol sprays and pump sprays without propellant gas) and hair mousses(aerosol mousses and pump mousses without propellant gas).

In a preferred embodiment, these preparations comprise

a) 0.1 to 10% by weight of the polymeric product according to theinvention

b) 20 to 99.9% by weight of water and/or alcohol

c) 0 to 70% by weight of a propellant

d) 0 to 20% by weight of further constituents

Propellants are the propellants customarily used for hair sprays oraerosol mousses. Preference is given to mixtures of propane/butane,pentane, dimethyl ether, 1,1-difluoroethane (HFC-152 a), carbon dioxide,nitrogen or compressed air.

A formulation for aerosol hair mousses preferred according to theinvention comprises

a) 0.1 to 10% by weight of the polymeric product according to theinvention

b) 55 to 99.8% by weight of water and/or alcohol

c) 5 to 20% by weight of a propellant

d) 0.1 to 5% by weight of an emulsifier

e) 0 to 10% by weight of further constituents

The emulsifiers used may be all emulsifiers customarily used in hairmousses. Suitable emulsifiers may be nonionic, cationic or anionic oramphoteric.

Examples of nonionic emulsifiers (INCl nomenclature) are laureths, e.g.laureth-4; ceteths, e.g. cetheth-1, polyethylene glycol cetyl ether;ceteareths, e.g. ceteareth-25, polyglycol fatty acid glycerides,hydroxylated lecithin, lactyl esters of fatty acids, alkylpolyglycosides.

Examples of cationic emulsifiers are or bromide (INCl Cetrimoniumchloride or bromide), hydroxyethylcetyldimonium phosphate (INClQuaternium-44), INCl Cocotrimonium methosulfate, INCl Quaternium-52,Quaternium-1 to x (INCl).

Anionic emulsifiers can, for example, be chosen from the group of alkylsulfates, alkyl ether sulfates, alkylsulfonates, alkylarylsulfonates,alkyl succinates, alkyl sulfosuccinates, N-alkoyl sarcosinates,alkylglycol alkoxylates, acyl taurates, acyl isethionates, alkylphosphates, alkyl ether phosphates, alkyl ether carboxylates,alpha-olefinsulfonates, in particular the alkali metal and alkalineearth metal salts, e.g. sodium potassium, magnesium, calcium, andammonium and triethanolamine salts. The alkyl ether sulfates, alkylether phosphates and alkyl ether carboxylates can have between 1 and 10ethylene oxide or propylene oxide units, preferably 1 to 3 ethyleneoxide units in the molecule.

A preparation suitable according to the invention for styling gels may,for example, have the following composition:

a) 0.1 to 10% by weight of the polymeric products according to theinvention

b) 60 to 99.85% by weight of water and/or alcohol

c) 0.05 to 10% by weight of a gel former

d) 0 to 20% by weight of further constituents

Gel formers which can be used are all gel formers customary incosmetics. These include slightly crosslinked polyacrylic acid, forexample Carborner (INCI), cellulose derivatives, e.g.hydroxypropylcellulose, hydroxyethylcellulose, cationically modifiedcelluloses, polysaccharides, e.g. xanthan gum, caprylic/caprictriglycerides, Sodium Acrylates Copolymer, Polyquaternium-32 (and)Paraffinum Liquidum (INCl), Sodium Acrylates Copolymer (and) ParaffinumLiquidum (and) PPG-1 trideceth-6, Acrylamidopropyl TrimoniumChloride/Acrylamide Copolymer, Steareth-10 Allyl Ether AcrylatesCopolymer, Polyquaternium-37 (and) Paraffinum Liquidum (and) PPG-1Trideceth-6, Polyquaternium 37 (and) Propylene Glycole DicaprateDicaprylate (and) PPG-1 Trideceth-6, Polyquaternium-7,Polyquaternium-44.

The polymeric products according to the invention can be used incosmetic preparations as conditioners. Examples are rinse-off andleave-on conditioner preparations.

The polymeric products according to the invention can also be used inshampoo formulations as setting and/or conditioning agents. Suitable asconditioning agents are, in particular, polymers with a cationic charge.Preferred shampoo formulations comprise

a) 0.05 to 10% by weight of the polymeric products according to theinvention

b) 25 to 94.95% by weight of water

c) 5-50% by weight of surfactants

c) 0-5% by weight of a further conditioning agent

d) 0-10% by weight of further cosmetic constituents

In the shampoo formulations, all anionic, neutral, amphoteric orcationic surfactants customarily used in shampoos can be used.

Suitable anionic surfactants are, for example, alkyl sulfates, alkylether sulfates, alkylsulfonates, alkylarylsulfonates, alkyl succinates,alkyl sulfosuccinates, N-alkoyl sarcosinates, acyl taurates, acylisethionates, alkylglycol alkoxylates, alkyl phosphates, alkyl etherphosphates, alkyl ether carboxylates, alpha-olefinsulfonates, inparticular the alkali metal and alkaline earth metal salts, e.g. sodium,potassium, magnesium, calcium, and ammonium and triethanolamine salts.The alkyl ether sulfates, alkyl ether phosphates and alkyl ethercarboxylates can have between 1 and 10 ethylene oxide or propylene oxideunits, preferably 1 to 3 ethylene oxide units, in the molecule.

Suitable compounds are, for example, sodium lauryl sulfate, ammoniumlauryl sulfate, sodium lauryl ether sulfate, ammonium lauryl ethersulfate, sodium lauroyl sarcosinate, sodium oleyl succinate, ammoniumlauryl sulfosuccinate, sodium dodecylbenzenesulfonate, triethanolaminedodecylbenzenesulfonate.

Suitable amphoteric surfactants are, for example, alkylbetaines,alkylamidopropylbetaines, alkylsulfobetaines, alkyl glycinates, alkylcarboxyglycinates, alkyl amphoacetates or amphopropionates, alkylamphodiacetates or amphodipropionates.

For example, cocodimethylsulfopropylbetaine, laurylbetaine,cocamidopropylbetaine or sodium cocamphopropionate can be used.

Suitable nonionic surfactants are, for example, the reaction products ofaliphatic alcohols or alkylphenols having 6 to 20 carbon atoms in thealkyl chain, which can be linear or branched, containing ethylene oxideand/or propylene oxide. The amount of alkylene oxide is about 6 to 60mol per mole of alcohol. Also suitable are alkylamine oxides, mono- ordialkyl alkanolamides, fatty acid esters of polyethylene glycols, alkylpolyglycosides or sorbitan ether esters.

Furthermore, the shampoo formulations can comprise customary cationicsurfactants, such as, for example, quaternary ammonium compounds, forexample cetyltrimethylammonium chloride or bromide (INCl Cetrimoniumchloride or bromide), hydroxyethylcetyldimonium phosphate (INClQuaternium-44), INCl Cocotrimonium methosulfate, INCl Quaternium-52.

In the shampoo formulations, customary conditioners can be used incombination with the polymers according to the invention to achievecertain effects. These include, for example, cationic polymers with theINCl name Polyquaternium, e.g. copolymers ofvinylpyrrolidone/N-vinylimidazolium salts (Luviquat™ FC, Luviquat™ HM,Luviquat™ MS, Luviquat™ Care, INCl: Polyquaternium-16,Polyquaternium44), copolymers of N-vinylpyrrolidone/dimethylaminoethylmethacrylate, quaternized with diethyl sulfate (Luviquat™ PQ 11, INCl:Polyquaternium-11), copolymers ofN-vinylcaprolactam/N-vinylpyrrolidone/N-vinylimidazolium salts(Luviquat™ Hold, INCl: Polyquaternium-46); copolymers of acrylamide anddimethyldiallylammonium chloride (Polyquaternium-7), cationic cellulosederivatives (Polyquaternium-4, -10). It is also possible to use cationicstarch derivatives (INCl: Starch Hydroxypropyltrimonium Chloride, CornStarch Modified), cationic guar derivatives (INCl: Hydroxypropyl GuarHydroxypropyltrimonium Chloride), cationic sunflower oil derivatives(INCl: Sunflowerseedamidopropyl Hydroxyethyldimonium Chloride),copolymers of acrylic acid, acrylamide and methacrylamidopropyltrimoniumchloride (INCl: Polyquaternium-53), Polyquaternium-32, Polyquaternium-28and others. In addition, it is possible to use protein hydrolysates, andconditioning substances based on silicone compounds, for examplepolyalkylsiloxanes, polyarylsiloxanes, polyarylalkylsiloxanes,polyethersiloxanes or silicone resins. Further suitable siliconecompounds are dimethicones, dimethicone derivatives or dimethiconecopolyols (CTFA) and aminofunctional silicone compounds such asamodimethicones (CTFA).

EXAMPLES Preparation Example Example 1

a) Preparation of Polymer (A)

The initial charge was heated under nitrogen gassing to 78° C. and leftfor 15 minutes at 78° C. Then, feed 1 was metered in over the course of2 hours, and feed 2 was metered in over the course of 2.5 hours. Themixture was after-polymerized for 2 hours and then feed 3 was metered inover the course of 15 minutes.

Initial Charge:

250 g of ethanol, cosm.

63 g of Pluriol A 11 R

100 g of feed 1

7.5 g of feed 2

Feed 1:

120 g of ethanol, cosm.

562 g of tert-butyl acrylate

188 g of methacrylic acid

Feed 2:

200 g of ethanol, cosm.

3 g of tert-butyl perpivalate (75% strength)

Feed 3:

240 g of ethanol, cosm.

3 g of tert-butyl perpivalate (75% strength)

The resulting polymer A had a solids content of 51.3%, a K value (1% inethanol) of 39.1 and an acid number (mg of KOH/g) of 80.1.

b) Mixing of (A) with Silicone (B)

In a 2 l four-necked flask, 243.7 g of the polymer obtained as in a) and13.84 g of polyalkoxylated silicone (Belsil DMC 6031, Wacker) werestirred at 78° C. for one hour under nitrogen gassing.

The resulting product had a solids content of 55.9%, a K value (1% inethanol) of 37.1 and an acid number (mg of KOH/g) of 81.6.

Comparative Example 1

For Comparative Example 1, the procedure was analogous to Example 1(polymer A and silicone B). However, the two components were stirred atroom temperature (20° C.) for 1 hour.

Performance Properties

a) Measurement of the Stiffness (Flexural Strength)

To measure the flexural strength, 3.0% strength by weight solutions ofthe polymeric products according to Example 1 and of Comparative Example1 were prepared. The flexural strength measurement was carried out on 5to 10 hair tresses (each about 3 g and 24 cm in length) at 20° C. and arelative humidity of 65%. The weighed dry hair tresses were dipped intothe 3% strength polymer solution, uniform distribution being ensured byimmersing and removing the tresses three times. The excess film formersolution was stripped off between the thumb and index finger and thetresses of hair were then carefully squeezed out by pressing betweenfilter papers. The hair tresses were then shaped by hand such that theyhad a round cross section. They were dried overnight in a climaticallycontrolled room at 20° C. and a relative humidity of 65%.

The tests were carried out in a climatically controlled room at 20° C.and a relative humidity of 65% using a tensile/compressive testingdevice. The tress of hair was placed symmetrically on two cylindricalrolls of the sample holder. Then, the hair tresses were bent 40 mmexactly in the middle from above using a rounded punch (breakage of thepolymer film). The force required for this was measured using a loadcell (50 N) and given in newtons.

b) Measuring the Curl Retention

To measure the curl retention, 1.8% strength by weight solutions of thepolymeric product according to Example 1 and of Comparative Example 1were prepared. The curl retention measurement was carried out asfollows: the washed, dry hair tresses were placed in 50% strengthethanol (ethanol abs./water dist. 1:1) at about 40° C. for 15 minutes.The thumb and index finger were used to press out the excess liquid andthe hair tresses were wound around a Plexiglas tube. The hair tresseswere then dried overnight at 65 to 70° C. After 15 minutes at roomtemperature, the hair was unwound. About 5 g of hair spray was sprayedon (from a distance of about 20 cm), during which the curl was rotated.Subsequently, it was dried in the lying position for 1 hour at roomtemperature.

The curl was hung up by one end and the curl length (Lo) was measured.The curl was placed into a climatically controlled chamber (25° C.,relative humidity 90%) and its length (Lt) after 15, 30, 60 and 90minutes, and also after 2, 3, 4, 5 and 24 hours was measured. The testwas carried out on at least 5 hair tresses.${{Curl}\quad{Retention}\quad{in}\quad\%} = {\frac{L - {Lt}}{L - {Lo}}*100}$

L=Length of the hair (15.5 cm)

Lo=Length of the hair after drying

Lt=Length of the hair following climatically controlled treatment

Table 1 gives the values of the flexural strength and curl retention ofExample 1 and Comparative Example 1. TABLE 1 Flexural strength in cN (3%by weight W.S. in ethanol abs.; 20° C. and relative humidity 65%) andcurl retention (%) Flexural Curl strength [cN] retention (%) ComparativeExample 1 79 78 Example 1 126 76

As the table shows, the flexural strength of the polymeric productaccording to the invention is significantly greater than that of thecomparative example whilst retaining the curl retention properties.Formulation Examples Mixing ratio Mixing ratio Mixing ratio Polymers 8:21:1 2:8 Polymeric 6.40% polymeric product 4.0% polymeric product 1.6%polymeric product product as in as in Example 1 as in as in Example 1/1.60% Luviskol Example 1 Example 1 Luviskol VA37E ™ 4.0% Luviskol 6.4%Luviskol VA37 ™ 0.74% AMP (2-amino-2- VA37E ™ VA37E ™ methylpropanol)0.46% AMP 0.19% AMP 51.26% ethanol 51.54% ethanol 51.81% ethanol 40.00%DME (dimethyl 40.0% DME 40.0% DME ether) Polymeric 6.4% polymericproduct 4.0% polymeric product 1.6% polymeric product product as in asin Example 1 as in as in Example 1/ 0.8% Luviskol K30 ™ Example 1Example 1 Luviskol 0.74% AMP 2.0% Luviskol K30 ™ 3.2% Luviskol K30 ™K30 ™ 52.06% ethanol 0.46% AMP 0.19% AMP 40.0% DME 53.54% ethanol 55.01%ethanol 40.0% DME 40.0% DME Polymeric 6.4% polymeric product 4.0%polymeric product 1.6% polymeric product product as in as in Example 1as in as in Example 1/ 2.0% Luviskol Plus ™ Example 1 Example 1 Luviskol0.74% AMP 5.0% Luviskol Plus ™ T 8.0% Luviskol Plus ™ Plus ™ 50.86%ethanol 0.46% AMP 0.19% AMP 40.0% DME 50.54% ethanol 50.21% ethanol40.0% DME 40.0% DME Polymeric 6.4% polymeric product 4.0% polymericproduct 1.6% polymeric product product as in as in Example 1 as in as inExample 1/ 2.67% Luviset P.U.R ™ Example 1 Example 1 Luviset 0.73% AMP6.67% Luviset 10.67% Luviset P.U.R. 50.20% ethanol P.U.R ™ P.U.R ™ 40.0%DME 0.46% AMP 0.19% AMP 48.87% ethanol 47.54% ethanol 40.0% DME 40.0%DME Polymeric 6.4% polymeric product 4.0% polymeric product 1.6%polymeric product product as in as in Example 1 as in as in Example 1/0.8% Ultrahold 8 ™ Example 1 Example 1 Ultrahold 8 0.82% AMP 2.0%Ultrahold 8 ™ 3.2% Ultrahold 8 ™ 51.98% ethanol 0.66% AMP 0.51% AMP40.0% DME 53.34% ethanol 54.69% ethanol 40.0% DME 40.0% DME Polymeric6.4% polymeric product 4.0% polymeric product 1.6% polymeric productproduct as in as in Example 1 as in as in Example 1/ 0.8% UltraholdExample 1 Example 1 Ultrahold StrongT 2.0% Ultrahold 3.2% UltraholdStrong 0.84% AMP StrongT StrongT 51.96% ethanol 0.71% AMP 0.59% AMP40.0% DME 53.29% ethanol 54.61% ethanol 40.0% DME 40.0% DME Polymeric6.4% polymeric product 4.0% polymeric product 1.6% polymeric productproduct as in as in Example 1 as in as in Example 1/ 0.8% Luviset CA66 ™Example 1 Example 1 Luviset CA66 0.82% AMP 2.0% Luviset CA66 ™ 3.2%Luviset CA66 ™ 51.98% ethanol 0.69% AMP 0.53% AMP 40.0% DME 53.31%ethanol 54.67% ethanol 40.0% DME 40.0% DME Polymeric 6.4% polymericproduct 4.0% polymeric product 1.6% polymeric product product as in asin Example 1 as in as in Example 1/ 0.8% Luviset CAN ™ Example 1 Example1 Luviset CAN 0.82% AMP 2.0% Luviset CAN ™ 3.2% Luviset CAN ™ 51.98%ethanol 0.70% AMP 0.54% AMP 40.0% DME 53.3% ethanol 54.66% ethanol 40.0%DME 40.0% DME Polymeric 6.4% polymeric product 4.0% polymeric product1.6% polymeric product product as in as in Example 1 as in as in Example1/ 0.8% Amphomer ™ Example 1 Example 1 Amphomer 0.88% AMP 2.0%Amphomer ™ 3.2% Amphomer ™ 51.92% ethanol 0.83% AMP 0.77% AMP 40.0% DME52.87% ethanol 54.43% ethanol 40.0% DME 40.0% DME

Hair sprays containing propane/butane 3.5 bar or propane/ butane 3.5 barwith added DME Mixing ratio Mixing ratio Mixing ratio Polymers 8:2 1:12:8 Polymeric product 6.4% polymeric product 4.0% polymeric product 1.6%polymeric product as in Example as in as in as in 1/Luviskol Example 1Example Example 1 VA37 1.6% Luviskol 14.0% Luviskol 6.4% LuviskolVA37E ™ VA37E ™ VA37E ™ 0.74% AMP 0.46% AMP 0.19% AMP 51.26% ethanol51.54% ethanol 51.81% ethanol 10.0% Pr/Bu 3.5 (propane/ 10.0% Pr/Bu 3.510.0% Pr/Bu 3.5 butane 30.0% DME 30.0% DME 3.5 bar) 30.0% DME Polymeric6.4% polymeric product 4.0% polymeric product 1.6% polymeric productproduct as in as in as in as in Example 1/ Example 1 Example 1 Example 1Luviskol K30 0.8% Luviskol K30 ™ 2.0% Luviskol K30 ™ 3.2% Luviskol K30T0.74% AMP 0.46% AMP 0.19% AMP 52.06% ethanol 53.54% ethanol 55.01%ethanol 40.0% Pr/Bu 3.5 40.0% Pr/Bu 3.5 40.0% Pr/Bu 3.5 Polymeric 6.4%polymeric product 4.0% polymeric product 1.6% polymeric product productas in as in as in as in Example 1/ Example 1 Example 1 Example 1Luviskol Plus 2.0% Luviskol PlusT 5.0% Luviskol PlusT 8.0% LuviskolPlusT 0.74% AMP 0.46% AMP 0.19% AMP 50.86% ethanol 50.54% ethanol 50.21%ethanol 40.0% Pr/Bu 3.5 40.0% Pr/Bu 3.5 40.0% Pr/Bu 3.5 Polymeric Notpossible 4.0% polymeric product 1.6% polymeric product product as in asin as in Example Example 1/ Example 1 110.67% Luviset Luviset P.U.R.6.67% Luviset P.U.R ™ P.U.R ™ 0.19% AMP 0.46% AMP 47.54% ethanol 48.87%ethanol 15% Pr/Bu 3.5 10% Pr/Bu 3.5 25.0% DME 30.0% DME Polymeric 6.4%polymeric product 4.0% polymeric product 1.6% polymeric product productas in as in as in as in Example 1/ Example 1 Example 1 Example 1 Luvimer100P 0.8% Luvimer 100P ™ 2.0% Luvimer 100P ™ 3.2% Luvimer 100P ™ 0.93%AMP 0.94% AMP 0.95% AMP 51.87% ethanol 53.06% ethanol 54.25% ethanol40.0% Pr/Bu 3.5 40.0% Pr/Bu 3.5 40.0% Pr/Bu 3.5 Polymeric 6.4% polymericproduct 4.0% polymeric product 1.6% polymeric product product as in asin as in as in Example 1/ Example 1 Example 1 Example 1 Ultrahold 8 0.8%Ultrahold 8 ™ 2.0% Ultrahold 8 ™ 3.2% Ultrahold 8 ™ 0.82% AMP 0.66% AMP0.51% AMP 51.98% ethanol 53.34% ethanol 54.69% ethanol 40.0% Pr/Bu 3.540.0% Pr/Bu 3.5 40.0% Pr/Bu 3.5 Polymeric 6.4% polymeric product 4.0%polymeric product 1.6% polymeric product product as in as in as in as inExample 1/ Example Example 1 Example 1 Ultrahold 10.8% Ultrahold 2.0%Ultrahold 3.2% Ultrahold Strong Strong ™ Strong ™ Strong ™ 0.84% AMP0.71% AMP 0.59% AMP 51.96% ethanol 53.29% ethanol 54.61% ethanol 40.0%Pr/Bu 3.5 40.0% Pr/Bu 3.5 40.0% Pr/Bu 3.5 Polymeric 6.4% polymericproduct 4.0% polymeric product 1.6% polymeric product product as in asin as in as in Example 1/ Example 1 Example 1 Example Luviset CA66 0.8%Luviset CA66 ™ 2.0% Luviset CA66 ™ 13.2% Luviset 0.82% AMP 0.69% AMPCA66 ™ 51.98% ethanol 53.31% ethanol 0.53% AMP 10.0% Pr/Bu 3.5 10.0%Pr/Bu 3.5 54.67% ethanol 30.0% DME 30.0% DME 10.0% Pr/Bu 3.5 30.0% DMEPolymeric 6.4% polymeric product 4.0% polymeric product 1.6% polymericproduct product as in as in as in as in Example 1/ Example 1 Example 1Example 1 Luviset ™ CAN 0.8% Luviset CAN ™ 2.0% Luviset CAN ™ 3.2%Luviset CAN ™ 0.82% AMP 0.70% AMP 0.54% AMP 51.98% ethanol 53.3% ethanol54.66% ethanol 20.0% Pr/Bu 3.5 20.0% Pr/Bu 3.5 20.0% Pr/Bu 3.5 20.0% DME20.0% DME 20.0% DME Polymeric 6.4% polymeric product 4.0% polymericproduct 1.6% polymeric product product as in as in as in as in Example1/ Example 1 Example 1 Example 1 Amphomer ™ 0.8% Amphomer ™ 2.0%Amphomer ™ 3.2% Amphomer ™ 0.88% AMP 0.83% AMP 0.77% AMP 51.92% ethanol52.87% ethanol 54.43% ethanol 40.0% Pr/Bu 3.5 40.0% Pr/Bu 3.5 40.0%Pr/Bu 3.5 Polymeric 6.4% polymeric product 4.0% polymeric product 1.6%polymeric product product as in as in as in as in Example 1/ Example 1Example 1 Example 1 Luviflex Silk ™ 0.8% Luviflex Silk ™ 2.0% LuviflexSilk ™ 3.2% Luviflex Silk ™ 0.88% AMP 0.83% AMP 0.77% AMP 51.92% ethanol52.87% ethanol 54.43% ethanol 40.0% Pr/Bu 3.5 40.0% Pr/Bu 3.5 40.0%Pr/Bu 3.5

Pump sprays Mixing ratio Mixing ratio Mixing ratio Polymers 8:2 1:1 2:8Polymeric 10.85% polymeric 6.74% polymeric 2.69% polymeric product as inproduct as in product as in product as in Example 1/ Example 1 Example 1Example 1 Luviskol VA37 2.66% Luviskol 6.66% Luviskol 10.64% VA37E ™VA37E ™ Luviskol ™ VA37E 1.27% AMP 0.79% AMP 0.32% AMP 85.22% ethanol85.81% ethanol 86.35% ethanol Polymeric 10.85% polymeric 6.74% polymeric2.69% polymeric product as in product as in product as in product as inExample 1/ Example 1 Example 1 Example 1 Luviskol K30 1.33% LuviskolK30 ™ 3.33% Luviskol K30 ™ 5.32% Luviskol K30 ™ 1.27% AMP 0.79% AMP0.32% AMP 86.55% ethanol 84.14% ethanol 83.69% ethanol Polymeric 10.85%polymeric 6.74% polymeric 2.69% polymeric product as in product as inproduct as in product as in Example 1/ Example 1 Example 1 Example 1Luviskol Plus 3.33% Luviskol Plus ™ 8.33% Luviskol Plus ™ 13.3% LuviskolPlus ™ 1.27% AMP 0.79% AMP 0.32% AMP 84.55% ethanol 89.14% ethanol90.21% ethanol Polymeric 10.85% polymeric 6.74% polymeric 2.69%polymeric product as in product as in product as in product as inExample 1/ Example 1 Example 1 Example 1 Luviset P.U.R. 4.43% Luviset11.1% Luviset 17.73% Luviset P.U.R ™ P.U.R ™ P.U.R ™ 1.27% AMP 0.79% AMP0.32% AMP 83.45% ethanol 81.37% ethanol 79.26% ethanol Polymeric 10.85polymeric product 6.74% polymeric 2.69% polymeric product as in as inproduct as in product as in Example 1/ Example 1 Example 1 Example 1Luvimer 100p 1.33% Luvimer 3.33% Luvimer 5.32% Luvimer 100P ™ 100P ™100P ™ 1.55% AMP 1.56% AMP 1.58% AMP 86.27% ethanol 88.37% ethanol90.41% ethanol Polymeric 10.85% polymeric 6.74% polymeric 2.69%polymeric product as in product as in product as in product as inExample 1/ Example 1 Example 1 Example 1 Ultrahold 8 1.33% Ultrahold 8 ™3.33% Ultrahold 8 ™ 5.32% Ultrahold 8 ™ 1.36% AMP 1.1% AMP 0.85% AMP86.46% ethanol 88.83% ethanol 91.14% ethanol Polymeric 10.85% polymeric6.74% polymeric 2.69% polymeric product as in product as in product asin product as in Example 1/ Example 1 Example 1 Example 1 Ultrahold1.33% Ultrahold 3.33% Ultrahold 5.32% Ultrahold Strong Strong ™ Strong ™Strong ™ 1.4% AMP 1.18% AMP 0.98% AMP 86.42% ethanol 88.75% ethanol91.01% ethanol Polymeric 10.85% polymeric 6.74% polymeric 2.69%polymeric product as in product as in product as in product as inExample 1/ Example 1 Example 1 Example 1 Luviset CA66 1.33% Luviset3.33% Luviset 5.32% Luviset CA66 ™ CA66 ™ CA66 ™ 1.36% AMP 1.15% AMP0.88% AMP 86.46% ethanol 88.78% ethanol 91.11% ethanol Polymeric 10.85%polymeric 6.74% polymeric 2.69% polymeric product as in product as inproduct as in product as in Example 1/ Example 1 Example 1 Example 1Luviset CAN 1.33% Luviset CAN ™ 3.33% Luviset CAN ™ 5.32% Luviset CAN ™1.37% AMP 1.17% AMP 0.9% AMP 86.45% ethanol 88.76% ethanol 91.09%ethanol Polymeric 10.85% polymeric 6.74% polymeric 2.69% polymericproduct as in product as in product as in product as in Example 1/Example 1 Example 1 Example 1 Amphomer 1.33% Amphomer ™ 3.33% Amphomer ™3.33% Amphomer ™ 1.47% AMP 1.38% AMP 1.28% AMP 86.35% ethanol 88.55%ethanol 92.7% ethanol Polymeric 10.85% polymeric 6.74% polymeric 2.69%polymeric product as in product as in product as in product as inExample 1/ Example 1 Example 1 Example 1 Luviflex Silk ™ 1.33% LuviflexSilk ™ 3.33% Luviflex Silk ™ 3.33% Luviflex Silk ™ 1.47% AMP 1.38% AMP1.28% AMP 86.35% ethanol 88.55% ethanol 92.7% ethanol

Hair spray formulation based on dimethyl ether 1.00% by weight LuviskolK30 ™ (BASF) 2.92% by weight polymeric product as in Example 1 0.92% byweight 2-amino-2-methylpropanol 0.10% by weight diisobutyl adipate (Ex.Crodanol DiBA from Croda Oleochemicals) 0.05% by weight isodecane 0.10%by weight perfume oil 0.05% by weight D-Panthenol USPT (BASF) 14.78% byweight  water, demineralized 36.08% by weight  ethanol 40.00% by weight dimethyl ether

Hair spray formulations based on isobutane and n-pentane A) 6.80%polymeric product as in Example 1 0.79% 2-amino-2-methylpropanol 14.20%n-pentane 2.40% n-butane 35.90% isobutane 39.91% ethanol B) 3.00%Ultrahold Strong ™ (BASF) 1.00% polymeric product as in Example 1 0.48%2-amino-2-methylpropanol 0.03% DOW Corning 190 ™ (Dow Corning) 14.20%n-pentane 2.40% n-butane 35.90% isobutane 42.99% ethanol

Shine spray 2.00% Luviset CA66 ™ (BASF) 2.00% polymeric product as inExample 1 0.46% 2-amino-2-methylpropanol 1.00% DOW Corning 556 (DowCorning) 0.10% niacinamide 0.20% D-Panthenol USP ™ (BASF) 14.20%n-pentane 35.90% n-butane 44.14% ethanol

Hair spay VOC 80 with HFC 152A 2.00% Luviset CA66 ™(BASF) 4.80%polymeric product as in Example 1 0.79% 2-amino-2-methylpropanol 56.60%ethanol 15.81% propellant 152a (Ex. Dymel 152a from DuPont) 20.00%dimethyl ether

Hair spray VOC 55 with vitamins 4.80% polymeric product as in Example 13.33% Luviset P.U.R. ™ 0.57% 2-amino-2-methylpropanol 0.10% niacinamide(Hoffmann-La Roche) 0.10% Panthenol USP ™ (BASF) 38.83% water,demineralized 12.27% ethanol 40.00% dimethyl ether

Sunscreen pump spray for hair 2.00% polymeric product as in Example 10.23% 2-amino-2-methylpropanol 2.00% Uvinul MS 40 ™ (BASF)(benzophenone-4) 95.77% ethanol

Hair repair 1.00% Luviskol K30 ™ (BASF) 4.00% polymeric product as inExample 1 0.48% 2-amino-2-methylpropanol 0.20% hydrolyzed wheat protein(Ex. Cropesol WT from Croda, Inc.) 0.50% D-Panthenol USP ™ (BASF) 5.00%1,2-Propylene Glycol USP ™ (BASF) 10.00% ethanol 78.82% water,demineralized

Shining gel for hair with UV protection Phase A 0.80% Carbopol 2001ETD ™ (Goodrich) 33.84% water, demineralized Phase B 5.00% Abil 200(Goldschmidt) 3.00% Karion FP (Merck KGaA) 3.00% 1,2-Propylene glycolUSPT (BASF) 1.00% Cremophor RH40T (BASF) q.s. preservative Phase C50.00% water, demineralized 0.50% Uvinul P25 ™ (BASF) (PEG-25PABA) 2.00%polymeric product as in Example 1 0.23% 2-amino-2-methylpropanol Phase D0.63% 2-amino-2-methylpropanol

Mascara Phase A 1.50% Cremophor A6 ™ (BASF) 1.50% Cremophor A25 ™ (BASF)2.00% stearic acid (Ex. Emersol 120 ™ from Henkel) 3.00% Imwitor 960 K ™(Hüls AG) 3.00% Softisan 100 ™ (Hüls AG) 1.50% Luvigel EM ™ (BASF)10.00% Dow Corning 345 ™ (Dow Corning) Phase B 4.00% polymeric productas in Example 1 0.46% 2-amino-2-methylpropanol 0.30% Germal 115 ™(Sutton) 72.24% water, demineralized Phase C 0.50% phenoxyethanol (Ex.Phenoxetol ™ from Nipa-Hardwicke)

Shampoo formulation 1.50% polymeric product as in Example 1 0.17%2-aminomethylpropanol 0.50% Luviskol K30 ™ (BASF) 10.00% Tego-Betaine L740.00% Texapon NSO 0.10% Euxyl K100 2.00% NaCl 45.73% water

Shampoo formulation with Luviquat Care ™ 1.80% polymeric product as inExample 1 0.21% 2-aminomethylpropanol 0.20% Luviskol K30 ™ (BASF) 7.70%Luviquat Care ™ (BASF) 10.00% Tego-Betaine L7 40.00% Texapon NSO 0.10%Euxyl K 100 2.00% NaCl 37.99% water

Clear lacquer 15.0% nitrocellulose 7.0% polymeric product as in Example1 2.4% camphor 4.5% palatinol A 7.0% isopropanol 8.0% methyl acetate8.0% ethyl acetate 14.0% ispropyl acetate 34.1% butyl acetate

Clear lacquer without nitrocellulose 23.0% polymeric product as inExample 1 7.0% Ketjenflex MH 2.4% camphor 4.5% palatinol A 8.0% methylacetate 8.0% ethyl acetate 14.0% isopropyl acetate 33.1% butyl acetate

VOC 55 hair spray 21.50% water 35.00% alcohol SD 40-B 0.95%aminomethylpropanol 8.00% polymeric product as in Example 1 0.20%D,L-panthenol 0.10% Uvinul ™ MC 80 (octyl methoxycinnamate) 0.10%Masil ™ SF 19 (dimethicone copolyol) 15.00% dimethyl ether 20.00%hydrofluorocarbon 152a

VOC 55 hair spray 34.10% water 52.00% alcohol SD 40-B 0.50%aminomethylpropanol 9.00% Luviset ™ P.U.R. polyurethane-1) 4.00%polymeric product as in Example 1 2.00% D,L-panthenol 0.10% Uvinul ™ MC80 (octyl methoxycinnamate) 0.10% Masil ™ SF 19 (dimethicone copolyol)

Unless expressly mentioned otherwise, all of the percentages given inthe examples are percentages by weight.

1. A process for the preparation of polymeric products, which comprisesi) polymerizing ethylenically unsaturated monomers (A-1) in the presenceof unsaturated polyalkylene glycols (A-2) ii) mixing the resultingpolymer with silicones (B) at a temperature of greater than or equal to40° C., in particular greater than or equal to 50° C.
 2. The processaccording to claim 1, wherein the silicones (B) are chosen from thegroup consisting of (B-1) silicones with at least one quaternized ornonquaternized amine function, (B-2) silicone resins, (B-3) siliconerubbers, (B-4) polyalkoxylated silicones and/or silicone-containingpolyurethanes (B-5).
 3. A polymeric product obtainable by mixing (A)polymers which are obtainable by free-radical polymerization of (A-1)ethylenically unsaturated monomers in the presence of (A-2) unsaturatedpolyalkylene glycols with (B) silicones at a temperature greater than orequal to 40° C., in particular greater than or equal to 50° C.
 4. Thepolymeric product according to claim 3, wherein the ethylenicallyunsaturated monomers (A-1) and the unsaturated polyalkylene glycols(A-2) are polymerized in the ratio 50 to 99.9% by weight of (A-1) and0.1 to 50% by weight of (A-2).
 5. The polymeric product according toclaim 3, wherein 99.5 to 70% by weight of polymer (A) and 0.5 to 30% byweight of silicones (B) are used.
 6. The polymeric product according toclaim 3, wherein the silicones are chosen from the group consisting of(B-1) silicones with at least one quaternized or nonquaternized aminefunction, (B-2) silicone resins, (B-3) silicone rubbers, (B-4)polyalkoxylated silicones and/or silicone-containing polyurethanes(B-5).
 7. The polymeric product according to claim 3, wherein themonomer (A-1) used is at least one compound of the formulaX—C(O)CR⁷═CHR⁶ where X is chosen from the group of radicals —OH, —OM,—OR⁸, NH₂, —NHR⁸, N(R⁸)₂ M is a cation chosen from the group consistingof: Na+, K+, Mg++, Ca++, Zn++, NH4+, alkylammonium, dialkylammonium,trialkylammonium and tetraalkylammonium; the radicals R⁸ may beidentical or different and are chosen from the group consisting of —H,C1-C40 linear or branched-chain alkyl radicals, N,N-dimethylaminoethyl,2-hydroxyethyl, 2-methoxyethyl, 2-ethoxyethyl, hydroxypropyl,methoxypropyl or ethoxypropyl. R⁷ and R⁶, independently of one another,are chosen from the group consisting of: —H, C₁-C₈ linear orbranched-chain alkyl chains, methoxy, ethoxy, 2-hydroxyethoxy,2-methoxyethoxy and 2-ethoxyethyl.
 8. The polymeric product according toclaim 3, wherein the monomers (A-1) are chosen from the group consistingof acrylic acid, methacrylic acid, ethylacrylic acid, methyl acrylate,ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate,t-butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, methylmethacrylate, ethyl methacrylate, propyl methacrylate and n-butylmethacrylate.
 9. The polymeric product according to claim 3, wherein themonomers (A-1) used are at least 2 compounds which are chosen from thegroup consisting of acrylic acid, methacrylic acid, ethylacrylic acid,methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate,isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, decylacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylateand n-butyl methacrylate.
 10. The polymeric product according to claim3, wherein the unsaturated polyalkylene glycols (A-2) used are compoundsof the formulaH₂C═CH—C_(c)H_(2c)—O—(C₂H₄O)_(a)(C₃H₆O)_(b)—R⁵ and/orH₂C═CH—C_(c)H_(2c)—O—(C₄H₈O)_(a)—R⁵ in which R⁵ is —H, —CH═CH₂,—CH₂)₅—CH═CH—(CH₂)_(t)—H, a straight-chain or branched alkyl grouphaving 1 to 12 carbon atoms, a straight-chain or branched alkoxy grouphaving 1 to 6 carbon atoms, a straight-chain or branched acyl grouphaving 2 to 40 carbon atoms, —SO₃M, a C₁₋₆-aminoacyl group optionallysubstituted on the amino group, —NHCH₂CH₂COOM, —N(CH₂CH₂COOM)₂, anaminoalkyl group optionally substituted on the amino group and on thealkyl group, a C₂₋₃₀-carboxyacyl group, a phosphono group optionallysubstituted by one or two substituted aminoalkyl groups,—CO(CH₂)_(d)COOM, —COCHR⁷(CH₂)_(d)COOM, —NHCO(CH₂)_(d)OH, —NH₂Y or aphosphate group the groups M, which are identical or different from oneanother, are hydrogen, Na, K, Li, NH₄ or an organic amine, R⁷ ishydrogen or SO₃M, d is in the range from 1 to 10, s may be 0, 1 to 10 tmay be 0, 1 to 10 a is in the range from 0 to 50, b is in the range from0 to 50, a+b is greater than 0, c is 0, 1, 2, 3 or4, Y is a monovalentinorganic or organic anion.
 11. A cosmetic preparation comprising apolymeric product according to claim
 3. 12. The cosmetic preparationwherein said products sets according to claim 11 as a setting agentand/or conditioning agent.
 13. A cosmetic preparation comprising a) 0.05to 20% by weight of the polymeric product according to claim 3 b) 20 to99.95% by weight of water and/or alcohol c) 0 to 79.5% by weight offurther constituents with the proviso that the amounts add up to 100%.14. The polymeric product according to claim 4, wherein 99.5 to 70% byweight of polymer (A) and 0.5 to 30% by weight of silicones (B) areused.
 15. The polymeric product according to claim 2, wherein thesilicones are chosen from the group consisting of (B-1) silicones withat least one quaternized or nonquaternized amine function, (B-2)silicone resins, B-3) silicone rubbers, (B-4) polyalkoxylated siliconesand/or silicone-containing polyurethanes (B-5).
 16. The polymericproduct according to claim 3, wherein the silicones are chosen from thegroup consisting of (B-1) silicones with at least one quaternized ornonquaternized amine function, (B-2) silicone resins, (B-3) siliconerubbers, (B4) polyalkoxylated silicones and/or silicone-containingpolyurethanes (B-5).
 17. The polymeric product according to claim 4,wherein the silicones are chosen from the group consisting of (B-1)silicones with at least one quaternized or nonquaternized aminefunction, (B-2) silicone resins, (B-3) silicone rubbers, (B-4)polyalkoxylated silicones and/or silicone-containing polyurethanes(B-5).
 18. The polymeric product according to claim 5, wherein thesilicones are chosen from the group consisting of (B-1) silicones withat least one quaternized or nonquaternized amine function, (B-2)silicone resins, (B-3) silicone rubbers, (B-4) polyalkoxylated siliconesand/or silicone-containing polyurethanes (B-5).
 19. The polymericproduct according to claim 2, wherein the monomer (A-1) used is at leastone compound of the formulaX—C(O)CR⁷═CHR⁶ where X is chosen from the group of radicals —OH, —OM,—OR⁸, NH₂, —NHR⁸, N(R⁸)₂ M is a cation chosen from the group consistingof: Na+, K+, Mg++, Ca++, Zn++, NH4+, alkylammonium, dialkylammonium,trialkylammonium and tetraalkylammonium; the radicals R⁸ may beidentical or different and are chosen from the group consisting of —H,C1-C40 linear or branched-chain alkyl radicals, N,N-dimethylaminoethyl,2-hydroxyethyl, 2-methoxyethyl, 2-ethoxyethyl, hydroxypropyl,methoxypropyl or ethoxypropyl. R⁷ and R⁶, independently of one another,are chosen from the group consisting of: —H, C₁-C₈ linear orbranched-chain alkyl chains, methoxy, ethoxy, 2-hydroxyethoxy,2-methoxyethoxy and 2-ethoxyethyl.
 20. The polymeric product accordingto claim 3, wherein the monomer (A-1) used is at least one compound ofthe formulaX—C(O)CR⁷═CHR⁶ where X is chosen from the group of radicals —OH, —OM,—R⁸, NH₂, —NHR⁸, N(R⁸)₂ M is a cation chosen from the group consistingof: Na+, K+, Mg++, Ca++, Zn++, NH4+, alkylammonium, dialkylammonium,trialkylammonium and tetraalkylammonium; the radicals R⁸ may beidentical or different and are chosen from the group consisting of —H,C1-C40 linear or branched-chain alkyl radicals, N,N-dimethylaminoethyl,2-hydroxyethyl, 2-methoxyethyl, 2-ethoxyethyl, hydroxypropyl,methoxypropyl or ethoxypropyl. R⁷ and R⁶, independently of one another,are chosen from the group consisting of: —H, C₁-C₈ linear orbranched-chain alkyl chains, methoxy, ethoxy, 2-hydroxyethoxy,2-methoxyethoxy and 2-ethoxyethyl.